Advances in Colloid and Interface Science 277 (2020) 102108

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Advances in Colloid and Interface Science

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Historical Perspective

Metalloporphyrinic metal-organic frameworks: Controlled synthesis

for catalytic applications in environmental and biological media
Sherif A. Younis a,b,c, Dong-Kwon Lim d, Ki-Hyun Kim a,⁎, Akash Deep e,⁎
a
Department of Civil and Environmental Engineering, Hanyang University, 222 Wangsimni-Ro, Seoul 04763, Republic of Korea
b
Analysis and Evaluation Department, Egyptian Petroleum Research Institute (EPRI), Nasr City, 11727 Cairo, Egypt
c
Liquid Chromatography and Water Unit, EPRI-Central Laboratories, Nasr City, 11727 Cairo, Egypt
d
KU-KIST Graduate School of Converging Science and Technology, Korea University,145 Anam-ro, Seongbuk-gu, Seoul 02841, Republic of Korea
e
Central Scientific Instruments Organization (CSIR-CSIO), Sector 30 C, Chandigarh 160030, India

a r t i c l e i n f o a b s t r a c t

Article history: Recently, as a new sub-family of porous coordination polymers (PCPs), porphyrinic-MOFs (Porph-MOFs) with
9 January 2020 biomimetic features have been developed using porphyrin macrocycles as ligands and/or pillared linkers. The
Available online 23 January 2020 control over the coordination of the porphyrin ligand and its derivatives however remains a challenge for engi-
neering new tunable Porph-MOF frameworks by self-assembly methods. The key challenges exist in the follow-
Keywords:
ing respects: (i) collapse of the large open pores of Porph-MOFs during synthesis, (ii) deactivation of unsaturated
Metal-organic frameworks (MOFs)
Metalloporphyrin coordination
metal-sites (UMCs) by axial coordination, and (iii) the tendency of both coordinated moieties (at peripheral
Metalloporphyrin-MOFs composites meso- and beta-carbon sites) and the N4-pyridine core to coordinate with metal cations. In this respect, this re-
Modulation strategies view covers the advances in the design of Porph-MOFs relative to their counterpart covalent organic frameworks
Catalysis applications (Porph-COFs). The potential utility of custom-designed porphyrin/metalloporphyrins ligands is highlighted.
Synthesis strategies of Porph-MOFs are also illustrated with modular design of hybrid guest@host composites
(either Porph@MOFs or guest@Porph-MOFs) with exceptional topologies and stability. This review summarizes
the synergistic benefits of coordinated porphyrin ligands and functional guest molecules in Porph-MOF compos-
ites for enhanced catalytic performance in various redox applications. This review shed lights on the engineering
of new tunable hetero-metals open active sites within (metallo)porphyrin-MOFs as out-of-the-box platforms for
enhanced catalytic processes in chemical and biological media.
© 2020 Elsevier B.V. All rights reserved.

Abbreviations: ABTS, 2,20-azinodi(3-ethylbenzothiazoline)-6-sulfonate; TDCPP, tetrakis(3,5-biscarboxyl-phenyl)porphyrin; 2,3-Dha, 2,3-dihydroxyterephthalaldehyde; 2,3-Dma, 2,3-

dimethoxyterephthalaldehyde; BOP, Bodipy-Porphyrinic-MOF; bpt, Biphenyl-3,4',5-tricarboxylate; BPY, 4,4′- bipyridyl; CE heating, Conventional Electrical Heating; cis-DCPP, 5,10-di(4-
carboxyphenyl)-15,20-diphenylporphyrin; COFs, Covalent-Organic Frameworks; COPs, Covalent-Organic Polymers; CPFs, Country Partnership Frameworks; CPs, Coordination Polymers;
CSD, Cambridge Structural Database; CTAB, Cetyltrimethylammonium bromide; CXL, CO2-expanded liquid; CZJ, Chemistry Department of Zhejiang University; DABCO, Diaz-abicyclo
[2.2.2]octane; DEF, N,N-diethyl formamide; DMA, N,N-dimethylacetamide; DMBPY, 2,2’-dimethyl-4,4’-bipyridine; DMF, N,N-dimethyl formamide; DMTP, 2,5-dimethoxyterephthaldehyde;
DPBDPM, Dipyridyl boron dipyrromethene; DPNI, N,N’-di-(4-pyridyl)-1,4,5,8- naphthalenetetracarboxydiimide; DPT, 3,6-di-4-pyridyl-1,2,4,5-tetrazine; DSSC, Dye-sensitized solar cells; ET,
Electron-transfer; EWG, Electron Withdrawing Groups; FePcS, Iron tetrasulfophthalocyanin; FTO, Fluorine-doped tin oxide; FTPFs, Fluorinated Trimetal-Porphyrin Frameworks; GOx,
Glucose oxidase; H3ImDC, 4,5-imid-azoledicarboxylic acid; HER, Hydrogen Evolution Reaction; HOMO/LUMO, Highest/ Lowest Occupied Molecular Orbital Energy Levels; HT, High
Throughput Method; Ils, Ionic Liquids; LBL, Layer-by-Layer; LPE, Liquid-Epitaxy; MCR, Methyl-coenzyme M reductase; MFS-MOFs, Multi-Functional Sites-Metal-Organic Frameworks;
MIL, Matérial Institut Lavoisier; MLs, Metalloligands; MMPFs, Metal/metalloporphyrin framework; MOFs, Metal-Organic Frameworks; MOM, Metal−Organic Materials; MOP, Metal–
Organic Polyhedron; MPs, Metalloporphyrins; MW, Microwave; NCP, N-confused porphyrins; NJNU, Nanjing Normal University; NPs, Nanoparticles; OAc, Acetate; OER, Oxygen
Evolution Reaction; OMS, Open Metal Sites; ORR, Oxygen Reduction Reaction; PAFs, Porous Aromatic Frameworks; PCN, Porous Coordination Network; PCPs, Porous Coordination
Polymers; PCTFs, Porphyrin-based Covalent Triazine Frameworks; PDT, Photodynamic therapy; PEG, Polyethylene Glycol; PEI, Polyetherimide; PIZA, Porphyrin Illinois Zeolite Analogue;
POFs, Permanent-Organic Frameworks; POMs, Polyoxometalates; Porph-COF, Porphyrinic-based Covalent-Organic Framework; Porph-MOFs, porphyrinic-based Metal-Organic
Framework; PPF, Porphyrin Pillared Frameworks; PSD, Post-synthetic Deprotection; PSE, Post-synthetic Exchange; PSM, Post-synthesis modification; PTT, Photothermal therapy; PVP,
Polyvinylpyrrolidone; Py-porph, 1,10,15,20 tetra-4-pyridyl-21H,23H-porphyrin; PyTPP, 5-pyridyl-10,15,20-triphenyl porphyrin; QDs, Quantum dots; RCSR, Reticular Chemistry Structure
Resource; chlorophyll-a, Reduced Graphene Oxide; RPM, Robust Porphyrin Materials; SALE, Solvent-assisted Linker Exchange; SBB, Supramolecular Building Blocks; SBUs, Secondary
Building Units; SC CO2, Supercritical CO2; SSA, Sequential Self-Assembly; T3MTPP, 5,10,15,20-tetrakis[3,4,5-tris(methylthio)phenyl]porphyrin; TAPP (or Tph), Tetrakis(4-aminophenyl) por-
phyrin; TATB, 4,4’,4’-s-triazine-2,4,6-triyl benzoate; TB(OH)2PP, 5,10,15,20-tetrakis(4-(dihydroxyboryl)phenyl)porphyrin; TBCPP, 5,10,15,20-tetrakis(3,5-biscarboxyl-phenyl)-
porphyrinate; tBuSi(OH)3, Tert-butylsilane triol; TCBPP, 5,10,15,20- tetrakis(4-carboxybiphenyl)porphyrin; TCP, 5,10,15,20-tetrakis(4-cyanophenyl)porphyrin; TCPEP, 5,10,15,20-
tetrakis(4-carboxyphenyl)ethynylporphyrin; TCPP (or T(p-CO2)PP), 5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin; tdc, 2,5-thiophenedicarboxylate; TDCPP, Tetrakis(3,5-biscarboxyl-
phenyl)porphyrin; TDPAP, Tetrakis(4,4-dipyridylamino-phenylene)porphyrin; TFB, 1,3,5-triformylbenzene; THB, Trihydroxybenzene; tImp, Imidazolyl-porphyrin ligand; TMPyP, meso-
tetra(N-methyl-4-pyridyl)porphyrin tetratosylate; TMSN3, Trimethylsilylazide; TOF, Turnover Frequency; TON, Turnover Number; TPP, Tetra(phenyl)porphyrinate; TPyP, 5,10,15,20-
tetra(4-pyridyl)porphyrin; TPyTa, Tris(4-pyridyl)1,3,5-triazine; trans-DCPP, 5,15-di(4-carboxyphenyl)-10,20-diphenylporphyrin; ttz, Tetrazole; ttzpp, Tetrakis[4-(2,3,4,5-tetrazolyl)phe-
nyl; UiO, University of Oslo; ULS, Ultrasonic; UMCs, Unsaturated metal centers; UTSA, University of Texas at San Antonio; ZIFs, Zeolitic-Imidazole Frameworks; ZJU, Zhejiang University.
⁎ Corresponding authors.
E-mail addresses: kkim61@hanyang.ac.kr (K.-H. Kim), dr.akashdeep@csio.res.in (A. Deep).

https://doi.org/10.1016/j.cis.2020.102108
0001-8686/© 2020 Elsevier B.V. All rights reserved.
2 S.A. Younis et al. / Advances in Colloid and Interface Science 277 (2020) 102108

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2. Categories of porous crystalline compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2.1. Covalent-organic frameworks (COFs) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2.1.1. In the area of catalytic applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
2.1.2. In the area of biology (e.g., drug delivery). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
2.2. Metal-organic frameworks (MOFs) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
3. Fundamentals of porphyrin derivative/isomer structures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
3.1. Porphyrin structures and their derivatives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
3.2. Coordination chemistry of metalloporphyrins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
3.3. Molecular porphyrin derivative synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
4. Engineering of porphyrinic-MOF frameworks (Porph-MOFs) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
4.1. Types of coordination frameworks with porphyrin/metalloporphyrin (MPs) linkers . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
4.2. Influence of porphyrins and secondary building unit (SBU) types on crystal geometry . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
4.2.1. Tetrakis(4-carboxyphenyl)porphyrin (TCPP)-based coordination frameworks . . . . . . . . . . . . . . . . . . . . . . . . . . 23
4.2.2. Tetra(4-pyridyl)porphyrin (TPyP)-based coordination frameworks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
4.2.3. Other customized metalloporphyrin-based coordination frameworks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
5. Diverse synthetic strategies for porphyrinic-coordination frameworks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
5.1. Synthetic approaches of (inorganic) SBU clusters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
5.2. Unsaturated metal center (UMC) sites within porphyrinic-MOF crystals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
5.3. Experimental synthetic aspects of Porph-MOFs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
5.4. Practical strategies in the design of porphyrinic MOF crystals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
6. Custom functionalization of Porph-MOFs and their composites for emerging applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
6.1. Custom-design of composite via pre- and post- synthetic functionalization strategies . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
6.2. Applications of functionalized Porph-MOF-based composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
6.2.1. Electrocatalysis and electrochemical sensors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
6.2.2. Photo-catalysis and photon-response activities . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
6.2.3. Other types of catalytic applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
7. Summary and remarks. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46
References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46

1. Introduction either by pre-synthesis or post-synthesis modification (PSM)

Over the past two decades, many research groups (Robson,
Kitagawa, Yaghi, and Férey and their co-workers) have contributed
to significant progress in developing numerous porous chemical ar-
chitectures by assembling different building units in one crystalline
network (or frameworks) with either ordered or disordered arrange-
ments [1]. The porous crystalline compound is a general term used to
describe these chemical architectures, which are composed of an
infinite array involving two central components on its backbone to
bridge: (i) connectors (as nodes) and (ii) ligands (as linkers) [2].
Based on the assembling nodes and linkage types within the building
backbone: the porous crystalline compounds can be divided into
two main categories, including covalent-organic frameworks
(COFs) and metal-organic frameworks (MOFs) (cf. Section 2 for
details) [3].
COFs exhibit low crystallinity (or an amorphous nature) and are
composed of organic building arrays interconnected by covalent
bonds, similar to conjugated microporous or hyper-branched polymers
[4,5]. However, MOFs (also known as porous coordination polymers:
PCPs) have highly ordered crystalline networks synthesized by coordi-
nations between organic ligands (linkers) and metal ions (metal clus-
ters/nodes referred to as secondary metal units (SBU)) through
partially reversible coordination bonds [6]. Given the thousands of pos-
sible coordinations between metal nodes and organic ligands with var-
ious distinct organic linkers (ditopic, tritopic, or quadrutopic), about one
million MOFs can be theoretically designed with thousands of topolo-
gies/geometries (as indicated by the Reticular Chemistry Structure Re-
source) [7]. According to the Cambridge Structural Database (CSD),
the number of synthesized MOFs has reached more than 80,000 to
date [8]. In principle, there is virtually no upper limit for the number
of possible MOF structures because they can be further functionalized
procedures [9,10].
Two main strategies have been applied to functionalize MOF/COF-
type molecular structures: (a) chemical functionalization of ligands
[11,12] and (b) physical encapsulation of functional (or nanoscale) ob-
jects into the cavities of the framework through non-covalent interac-
tions [13,14]. In coordination chemistry, versatile organic linkers have
been employed for the incorporation of various functionalities (e.g.,
acidity/basicity and coordination/chemical active sites) into the frame-
works of the prefabricated MOFs/COFs skeleton by pre-synthesis and
PSM procedures [5,13]. In some cases, functionalized organic ligands
can prevent or inhibit the crystal engineering of the framework if they
are pre-modified with thermally labile moieties (e.g., hydroxyls or car-
boxylic acids). Those labile groups show metal-coordinating character-
istics that interfere or compete with the coordination connectivity for
the PCP-type MOF crystals formation [15]. Similarly, utilization of PSM
routes (known as “ship in the bottle” and “bottle around the ship”;
Figs. 1a, b) is still a challenging task for controlled immobilization of
functional guest matrices in PCP networks to produce composite struc-
tures with designed features [13,16]. This was attributed to the com-
plexity of synthetic parameters and the effects of the PSM procedure
on the homogeneity of the composite products (see details in
Section 6.2).
Recently, the potential utility of metalloligand (ML) units has been
emphasized in a novel one-pot strategy for facile functionalization of
MOFs/COFs-type architectures (e.g., aldehyde functionalized Cu(I)-
bisphenanthroline tetrafluoroborate as ML linker in woven COF-505)
[17,18]. In this respect, a great deal of attention has been paid toward
the formulation of a porphyrin (C20H14N4) scaffold (Fig. 2) as an emerg-
ing powerful ML option [19,20]. The principal porphyrin macrocycle can
be easily adjusted to afford pendant donor functional moieties available
for polymeric coordination complexes in both natural and synthetic
 S.A. Younis et al. / Advances in Colloid and Interface Science 277 (2020) 102108
Fig. 1. Two main strategies used to prepare guest@PCP composites. (a) Ship in bottle and (b) bottle around ship.
systems via the exocyclic substituents on the 1–8 and α–δ peripheral ar-
rangement [21]. In addition, it is noted that (metallo)porphyrin (MPs)
molecules have unique cyclic chemical structures with an extensively
delocalized 2D π-system suitable for enhanced electron-transfer (ET)
reactions [22]. Thus, a variety of redox states can be achieved in MPs
with minimal structural change via numerous electron oxidation (or re-
duction) processes on their peripheral functionalities [23]. This would
ultimately facilitate the design and synthesis of a novel class of
coordination-driven porous framework solids (denoted as Porph-
based CPs to cover both COFs and MOFs). As a result, large amounts of
porphyrin and its metallated derivatives (Fig. 2) have been synthesized
artificially and examined for promoting supramolecular assembly of nu-
merous functional Porph-PCPs frameworks [18,19,24–26].
In 1994, the first genuine MP-based molecular sieve-type 3D coordi-
nation polymer (CP) framework was prepared by direct inter-
coordination of M(TPyP) (TPyP (or Tph) = 5,10,15,20-tetra(4-pyridyl)
porphyrin with M = Co, Zn or Mn)[27]. Concurrently, the designed 3D
M(TPyP)-based coordination framework of an open but remarkably ro-
bust honeycomb structure was found to have 0.6-nm-wide lattice chan-
nels. An attractive TCPP-like porphyrin platform (TCPP =5,10,15,20-
tetrakis(4-carboxyphenyl)porphyrin) was proposed in 1996 as a versa-
tile ligand for supramolecular synthesis of multi-porphyrin arrays [28].
Nonetheless, the potential efficacy of the TCPP ligands to form an open
2D CP lattice (Fig. 2) was proven in 1999 by Goldberg and co-workers
though self-organization of widely H-bonded non-interpenetrating por-
phyrin networks [29]. The formed 2D polymers having an M(TCPP)
structure exhibited an unusual porphyrin-sieve assembly consisting of
a tightly stacked coinciding arrangement of open arrays with wide
inter-porphyrin voids and 1.5-nm-wide vertical channels. These earlier
studies validated the benefits of M(TCPP)- and M(TPyP)-related MP
molecules in the engineering of multi-functional site (MFS)-based CPs
frameworks like Porph-MOFs [30]. This was attributed to the central
metal of the MP monomers, which supported either metal-centered
ET reactions (coordinatively saturated) or linker-centered reactions
(coordinatively unsaturated) to carry out many catalytic applications
[31]. Coordinatively unsaturated Porph-MOFs can be synthesized both
from ligation of auxiliary functional (COOH or NH) moieties of M
(TCPP)- and M(TPyP)-related MP ligands to an open site on the unsatu-
rated metal centers (UMCs) and from outer-sphere coordination of the
MPs to an exocyclic metal site [23]. Remarkably, UMCs formed both in
3
the MP core and the SBU-based open metal sites (OMS) can be used
as scaffolds to custom-control immobilization of various guest mole-
cules such as nanoparticles, active drugs, or conducting substrates
within Porph-MOF frameworks [15]. Thus, the choice of metal sites
(UMCs or OMS) allows for control over stoichiometry and geometry of
the designed Porph-MOFs, which can be utilized in theranostic applica-
tions and in natural bioprocesses.
In 1998, the so-called porous coordination polymers (CPs) were
classified into three-generations: (1) the 1st generation frameworks
have unstable microporous architecture sustained only with guest mol-
ecules to irreversibly collapse upon the removal of such guest mole-
cules; (b) the 2nd generation frameworks have stable and robust
porous architecture with permanent porosity (i.e., no guest molecules
in the pores); and (c) the 3rd generation frameworks have flexible
and dynamic architecture (i.e., channels or pores can be reversibly
changed) based on the external stimuli (e.g., electric field, light, or
guest molecules) [32]. In fact, most inorganic-based porous frameworks
constructed by covalent bonds are categorized as the 2nd generation
porous coordination frameworks. From this point-of-view, the prepara-
tion of Porph-based CPs crystals in either COF or MOF architecture cur-
rently appears promising as they can mimic the green nature of
porphyrin molecules with multiple functionalities (i.e., in heme B and
in chlorophyll a; cf. Section 3 for details). Nonetheless, controlled engi-
neering of new Porph-based CPs and prediction of their coordination
geometries still remain as challenges in scientific research. This is
mainly because most of the reported Porph-based CPs are assembled
from TPyP and TCPP ligands without considering other porphyrin deriv-
atives (Scheme 1) [33,34]
With the advent of porous MOF crystal engineering, the controllable
design of multidisciplinary Porph-MOF frameworks is becoming feasi-
ble with the advent of synthetic procedures. However, to the best of
our knowledge, no comprehensive reviews have yet reported on how
porous CPs (like MOFs) can be custom-designed or functionalized
based on (metallo)porphyrin building units. It is important to under-
stand how the coordination interlinkage can be developed either
when MP-based derivatives are used as functionalized guests (e.g.,
MP@MOFs composite) or building blocks in the crystalline frameworks
(e.g., Porph-MOFs design). In this respect, our review focused on a de-
scription of various strategies for controlled synthesis and development
of porous Porph-PCPs crystals with a defined topology. To this end, this
4 S.A. Younis et al. / Advances in Colloid and Interface Science 277 (2020) 102108

Fig. 2. Basic porphyrin structure and expected modified routes. Most commonly, porphyrin bearing pyridyl (TPyP) and carboxylate (TCPP) with approximate square-planar symmetry
(left) and space-filling illustrations of the honeycomb and stacked-layered 2D structure (right) used in the construction of extended Porph-PCP frameworks. Adapted from [29].

work should shed light on: (1) the historical development of Porph-
MOFs materials, (2) the fundamentals of synthetic porphyrin molecules
and the recent progress in molecular synthesis of porphyrin isomers/de-
rivatives along with metallated structures (properties and functionali-
ties), (3) the key challenges in self-assembly of Porph-MOFs crystals,
and (4) the current and future progress in crystal engineering of
Porph-MOFs based on deliberate control of synthesis parameters. We
aim to overcome the limitations encountered in material homogeneity,
axial coordination on the porphyrin metal-center, and fragility of crys-
tals toward loss of occluded solvent to tune crystal topology, shape,
and functionality of Porph-MOFs in large scale production. Finally, we
highlighted the most commonly applied post-synthesis modification
strategies for the controlled formulation of guest-host hybrid systems
(i.e., MFS-based Porph-MOFs composites) for maximizing specific per-
formances in their applications (such as photocatalysis and electro-
chemical sensing).
2. Categories of porous crystalline compounds
Recent advances in materials science have motivated the growth of
two fundamental categories of porous crystalline materials, including
COFs and MOFs.
2.1. Covalent-organic frameworks (COFs)
In 1916, Gilbert N. Lewis published his seminal article on chemical
bonding, “The Atom and the Molecule”, on which he later based the out-
line of “The Covalent Bond” to describe strong chemical interactions be-
tween atoms to form molecules [35]. Since then, materials scientists
have exploited these concepts to develop covalent molecular chemistry
for designing discrete microcrystalline COFs with varying characteristic
geometries based on organic synthons with reticular structures (Table 1
& Fig. 3). To date, control over the synthetic methodology has matured
for the design of various forms of COF single-crystals in a well-defined
geometry based on strong covalent interactions (e.g., imine linkage N
100 kcal/mol) [36,37]. In general, covalent bonds can be classified into
seven types in terms of the linkages they form within COF frameworks:
(i) boroxine B–O (borosilicate, boronate ester, and spiroborate), (ii) B=
N (borazine), (iii) N=N (azodioxy), (iv) imine C=N (hydrazine and
squaraine), (v) C=Naromatic (phenazine and triazine), (vi) imide C–N
(amide and β-ketonamine), and (vii) alkene C=C [38]. Overall, the 2D
conjugated Porph-COFs have been prepared for various catalytic appli-
cations based on different coupling reactions (e.g., Suzuki–Miyaura cou-
pling, alkyne–alkyne homocoupling, Yamamoto homo-coupling, alkyne
trimerization, Sonogashira–Hagihara cross coupling, and oxidative cou-
pling reactions) [39,40]. The Schiff base chemistry can also be employed
 S.A. Younis et al. / Advances in Colloid and Interface Science 277 (2020) 102108 5

Scheme 1. Porphyrin-based organic ligand structures. Reproduced from [97,129].

to control the design of imine-based conjugated Porph-COFs with -C=
N- linkage using amine-based porphyrin ligands and aldehyde linkers
[41–43]. In fact, it was reported that imine-linked Porph-COFs can also
be designed from aldehyde-substituted porphyrin ligand (e.g., 5,10,15,
20-tetrakis(4-benzaldehyde)porphyrin) and aromatic amine linkers
which can be applied for adsorption of CO2 or storage of sulfur in
lithium-sulfur batteries [44,45]. Accordingly, various imine-based
Porph-COFs can also be synthesized with different functionalities and
topologies by altering the aldehyde linkers or the core of amine-
porphyrin ligands. For example, COF-1 ((C3H2BO)6·(C9H12)1, P63/mmc)
—the first crystalline COF—is entirely composed of highly ordered, self-
assembled 1,4-benzene-diboronic acid (C6H4[B(OH)2]2) organic ligands
interconnected by boroxine (B−O) covalent linkages. Self-assemblies of
diboronic acid with 2,3,6,7,10,11-hexahydroxytriphenylene (HHTP,
C18H6(OH)6) monomers by a molecular dehydration reaction resulted
in mesoporous 2D COF-5 “C9H4BO” with P6/mmm single-crystals (Fig.
3) [46]. Five imine-linked Porph-COFs have been prepared by polycon-
densation reaction of copper-tetra(p-amino-phenyl)porphyrin (Cu-P)
with the mixtures of 2,3,5,6-tetrafluoroterephthalaldehyde (TFPh) and
terephthalaldehyde linker at varying molar ratios (CuP-TFPhX, x
(molar ratios) = 25, 50, 75, and 100) under solvothermal conditions
[47]. These prepared imine-linked Porph-COFs exhibited different po-
rosities and functionalities while retaining similar crystallinity.
In a recent milestone of the 20 th century, the formation of a
shape-permanent organic cage Porph-COF (also referred to as Por-
phyrin organic Framework: POF) architecture has been developed
using stable rich-electronic conjugated arrays of metalloporphyrin
ligand (i.e., MP) backbones (Figs. 3 and 4) [4,36]. Retrosynthesis of
functional MPs as a natural building block (e.g., COF-66 and COF-K:
Fig. 3(b)) can lead to the production of highly active and biologically
benign porous Porph-COF (POF) networks, which are receiving
widespread attention in medical therapy [48,49]. The union between
6 S.A. Younis et al. / Advances in Colloid and Interface Science 277 (2020) 102108

Table 1
List of organic building units and linkage units utilized for construction of COF and MOF frameworks. [35,38,331].

Order Organic Building/Linker Units

[a] Organic Building Units
1 Porphyrin builder units

2 Aromatic builder units

3 Other builder units

 S.A. Younis et al. / Advances in Colloid and Interface Science 277 (2020) 102108
[b] Organic Linkage Units
4
covalent and mechanical linkages in metallated Porph-COF nets may
show the enhanced potential for the development of molecularly
woven structures. For example, COF-K (Fig. 3b) with eclipsed topol-
ogy structure (potential woven material) was constructed via a
Schiff-base reaction from 5,10,15,20-tetrakis(4’-aminophenyl) por-
phyrin (linker) and 3,6-diformyl-9-ethylcarbazole (nonlinear con-
nector) [50]. As such, metallated Porph-COF materials are found to
have remarkable flexibility (resilience) with enhanced dynamic
crystallinity and chemical stability relative to conventional COFs/
MOF products when explored for environmental applications in
aqueous systems [35,37]. The organic analogs of Porph-COFs (Fig.
4) are capable of maintaining intrinsic molecular functionalities
and unique pore metrics within the frameworks, suggesting their
potential utilization in many environmental/catalytic applications
[51,52]. In this regard, Porph-COF networks also can improve semi-
conducting or luminescent emission properties for catalytic applica-
tions due to the highly electron-rich (i.e., 18 π- conjugation) MP
skeleton with accessible UMCs [53,54]. These UMCs sites serve as
OMSs in the (metallo)porphyrin channel walls of MOFs, while
MOFs are stabilized by weak coordination bonds [35]. Thus, Porph-
COFs can show higher stability than MOF frameworks in different
applications, as described below.
2.1.1. In the area of catalytic applications
A highly porous 3D covalent-porphyrinic framework, denoted as
crystalline CPF-2, was synthesized using solvothermal condensation of
a metal-free tetrakis(4-aminophenyl)-21H,23H-porphyrin “TAPP”
linker with trigonal 1,3,5-triformylbenzene (TFB) as the interlinkage re-
agent via imine linkages [55]. Based on the reticular chemistry principle,
porous CPF-2 was post-metallated with manganese (Mn (II)) and cobalt
(Co(II)) ions (M-CPF-2; M =Mn(II) or Co(II)) as accessible active OMSs
to tune heterogeneous catalysis reactions. The reported catalytic data
indicated that the Co-CPF-2 catalyst exhibited very high stability (15 cy-
cles) and selectivity (up to 93%) toward the aerobic epoxidation of 1,2-
epoxyethylbenzene styrene olefins under mild conditions, with a N 99%
7
conversion rate and 3434 h-1 turnover frequency (TOF) [4,55]. Likewise,
two organocatalytic CPFs isomers (2,3-DhaTph and 2,3-DmaTph) simi-
lar to that above were synthesized using TAPP (also known as Tph)
linkers interconnected with either 2,3-dimethoxyterephthalaldehyde
(2,3-Dma) or 2,3-dihydroxyterephthalaldehyde (2,3-Dha) via a Schiff-
base reaction (Fig. 5 (a)) [56]. It was found that hydroxyl-containing
CPFs (2,3-DhaTph) constitute both active acidic (phenolic) and basic
(porphyrin) sites with higher catalytic stability. In addition, the ob-
tained 2,3-DhaTph isomer exhibited enhanced crystallinity, stability,
and porosity due to the existence of neighboring hydroxyl groups that
form intramolecular hydrogen bonds (O-H···N=C), which efficiently
stabilized the imine linkage. The acid/base properties of 2,3-DhaTph
(hydroxyl-containing CPFs) efficiently catalyze the acid hydrolysis
of benzaldehyde and dimethyl acetal followed by basic condensation
with malononitrile to produce a 92% yield of 2-
benzylidenemalononitrile in 90 min at 80 ∘C up to 5 cycles (Fig. 5(b-
c)) [56]. More recently, Diercks et al. developed a new 2D Porph-COF
(called COF-366-Co) with a reticular electronic tuning using Co(TAPP)
interconnected with 1,4-benzenedicarboxaldehyde (BDA). The ori-
ented COF-366-Co thin film exhibited a remarkable enhancement in
the catalytic reduction of CO2 to CO on a Co(II) UMC site of a porphyrin
ring with a faradaic efficiency of 87% (i.e., 9-times improvement) as
compared to traditional microcrystalline COFs [54]. In a similar manner
to the above Porph-COFs, a new Porph-COF thin film catalyst (referred
to as FeDhaTph-COF) was synthesized on carbon cloth by the Schiff-
base reaction of Fe(III) chloride-TAPP (Fe(TAPP)Cl with electroactive
iron sites) with 2,5-Dha [57]. The prepared FeDhaTph-COF demon-
strated effective electrocatalytic performance for the reduction of CO2
to CO with a high TOF of N 600 h-1 mol-1 (average faradic efficiency
80%) due to the redox couples of Fe-UMC active sites (Fe(II/I) and Fe
(I/0)). More recently, a new Porph-COF (A2B2-Por-COF) was synthe-
sized successfully via the self-polycondensation of an A2B2 porphyrin
monomer (4′,4‴-(10,20-bis(4-aminophenyl)porphyrin-5,15-diyl)bis-
(([1,1′-biphenyl]-4-carbaldehyde)) in a mixed solvents systems for 7
days in the presence of acetic acid as catalyst [58]. This A2B2-Por-COF
8 S.A. Younis et al. / Advances in Colloid and Interface Science 277 (2020) 102108

Fig. 3. Schematic of topological design and reticular synthesis of COF frameworks. (a) Illustration of advances from Lewis’ original concept of the covalent bond to the development of 2D
and 3D COFs, as well as weaving and Porph-COFs frameworks reproduced from [35,54,366,367]. (b) Reticulation synthesis of the desired COF topology [e.g., COF-66:1) topology selection,
2) knowing the fundamental geometric units, 3) choosing the equivalent building molecules, 4) deriving connectivity nets, and 5) reticulating the desired COF geometry [35]] and COF-K
woven structure[50].

showed excellent visible-light absorption capability and high thermal/
chemical stability (e.g., up to 5 cycles) along with outstanding catalytic
activities towards oxidation of sulfides (98% conversion) and
Knoevenagel condensation (N99% conversion) processes.
It is noted that the efforts to design 3D Porph-COFs have been
made very scantily relative to 2D Porph-COFs. For example, in
2017, two types of 3D Porph-COFs were synthesized for the first
time by [4 + 4] imine condensation reactions between 5,10,15,20-
tetrakis(4-benzaldehyde)porphyrin (free and Cu-based porphyrin
ligands: p-Por-CHO and p-CuPor-CHO) and Tetra(p-aminophenyl)
methane (TAPM) in a mixture of solvents (e.g., dichlorobenzene,
butanol, and 6 M aqueous acetic acid) at 120°C for 7 days [59]. Re-
markably, both 3D Porph-COFs (i.e., 3D-Por-COF and 3D CuPor-
COF) showed pts net topology (Pmc21 space group) with tunable
microporous structures and high surface areas (1335 – 1398 m2.
g-1) along with high thermal/chemical stability in water and alkali
systems. In addition, those COFs exhibited good photo-electric sen-
sitivity to be employed as heterogeneous catalysts for generating
singlet oxygen upon photoirradiation at λ = 500 nm (94% photo-
catalytic efficiency up to 3 cycles stability). The control synthesis
of 3D imine-linked Co-Porph-COF (Co-COF-Py-rGO) was also car-
ried out via polymerization of cobalt(II)-tetra(phenyl)porphyrin
with amine substituent and terephthalaldehyde onto functional-
ized reduced graphene oxide with 4-styrylpyridine group (Py-rG)
[60]. In this case, the 4-styrylpyridine functionality acted as struc-
tural nodes to link Co-Porph-COF onto rGO and to grow a unique
3D architecture (3D CoCOF-Py-0.05rGO). Such a graphene-based
Porph-COF hybrid catalyst exhibited high catalytic activity in oxygen
reduction (33%) with satisfactory stability (after 30, 000 s) due to the
3D structure. In 2019, two new 3D Porph-COFs (PCOF-1 and P-COF-2)
with high crystallinity (pts topology) and rigidity were also reported
to exhibit enhanced electrocatalytic activity towards oxygen evolu-
tion reactions [61]. These PCOF-1 and P-COF-2 catalysts were con-
structed via imine-condensation reaction of rigid tetrahedral T 4
linker (3,3’,5,5’-tetrakis(4-formylphenyl)bimesityl) with two por-
phyrin ligands containing tetramine units (5,10,15,20-tetra(4-
aminophenyl)porphyrin and 5,10,15,20-tetra(4-aminobiphenyl)
porphyrin). The high crystallinity and rigidity of the prepared 3D
Porph-COFs should be attributed to the strong steric effects from
the existence of six methyl groups in the tetrahedral T 4 linker,
which limited the framework rotation to the plane. The potential of
3D Porph-COFs as biocatalysis was also demonstrated through the
encapsulation of PCOF-1 and PCOF-2 with ferric iron in the porphyrin
centers (PCOF-1Fe and PCOF-2Fe). Accordingly, they exhibited
enhancedcatalytic oxidation toward 2,2’-azinodi(3-ethylbenzo-
thiazoline)-6-sulfonate (91%; Kcat =32.4 – 3.69 min-1) and 3,3’,5,5’-
tetramethylbenzidine (93%; %; K cat =3.8 – 2.44 min-1 ) substrates
with good stability (e.g., up to 3 cycles).
 S.A. Younis et al. / Advances in Colloid and Interface Science 277 (2020) 102108 9

Fig. 4. Synthesis pathway of a porphyrin based on 2D COFs (ZnP–COF, COF-66 & COF-366) and their properties. Reproduced from [304,366].

2.1.2. In the area of biology (e.g., drug delivery)
Researchers have started to focus on utilizing COFs in this field in the
last few years, and the first report was published in 2011 [62]. These au-
thors designed a highly porous ordered structure of a covalently linked
framework (such as 2D PAF-6 also referred to as COP-1) with π-π stack-
ing via a one-step polymerization of piperazine with cyanuric chloride.
PAF-6 was found to possess a drug release ability toward ibuprofen
(IBU) drug molecules that outperformed nanomaterials like MCM-41
[63]. Following this, Bai and co-workers (2016) provided a new route
to produce low cytotoxic and biocompatible nanoscale COFs for phar-
maceutical applications, especially for anticancer therapy [64]. In this
work, two nanoscale PI-n-COFs materials (PI-3-COF and PI-2-COF)
were prepared using solvothermal condensation of 1,3,5-
triformylbenzene (aldehyde linker) with amine building units (either
4,4'-biphenyldiamine or 2,4,6-Tris(4-aminophenyl)-1,3,5-triazine).
Both of the prepared PI-n-COFs showed high activity as in-vitro
nanocarriers for anticancer drugs (5-fluorouracil “5-FU,” captopril, and
ibuprofen) with controlled release performance [64]. The lower
cytotoxicity and biocompatibility of PI-n-COFs were confirmed by har-
vesting 80% viable MCF-7 breast cancer cells in the presence of free
PI-n-COFs at maximum dosing of 200 mg/ml for 24 h. Therefore, recent
attempts have also been made to predict the performance of biomedical
Porph-COFs (with respect to in-vitro and in-vivo biocompatibility with
physicochemical stability and low reactivity in physiological media)
for biomedical purposes to promote in-vivo disease therapy. Among re-
cent attempts, porphyrin-based covalent triazine frameworks (PCTFs)
10 S.A. Younis et al. / Advances in Colloid and Interface Science 277 (2020) 102108

Fig. 5. Synthesis schemes of various Porph-MOFs based on TPyP (or Tph) porphyrin ligand and their applications: (a) The synthesis of CPF isomers frameworks (2,3-DhaTph and 2,3-
DmaTph) by the Schiff-base condensation of TAPP (or Tph) and 2,3-Dha/2,3-Dma (the catalytically active porphyrin and catecholic –OH groups are shown in coral and cyan colors,
respectively). (b) Kinetics of the cascade reaction. (c) Comparison of the recyclability studies performed for 2,3-DhaTph and 2,3-DmaTph [56]. (d) Preparation scheme of 2,5-DhaTph
and functionalized Tph–DMTP–COP (porphyrin-based COP-PEG) for PDT and PTT antitumor efficacy ([48,49]).

were synthesized by Luo et al. [65] via a Friedel–Crafts reaction of
tetraphenylporphyrin (TPP and manganese (Mn)-TPP) with cyanuric
chloride. Encouraged by their low-toxicity and micro/mesoporosity
(0.7-4.2 nm), the prepared PCTF and Mn-PCTF allowed for IBU drug
loading capacity (after 12h) of 19 and 23 wt%, respectively with a
good in vitro release profile (90 -95%) that was higher than MCM-41
nanocapsules and PI-COFs [65]. More recently, nanoscale low-toxic 2D
Porph-COFs with anticancer efficacy were constructed for the first
time by a solution-based aging method at room temperature (Fig. 5d)
[48]. The 2D Porph-COF was prepared from the aging of both TAPP (or
Tph) and 2,5-Dha (referred to as 2,5-DhaTph) in CH2Cl2 and CHCl3 in
the dark for 24 h. The biocompatibility was verified by a standard 3-
(4,5-dimethythiazol-2-yl)-2,5-diphenyl tetra-zolium bromide assay
(90% alive cell after 24 h). The obtained 2,5-DhaTph COF was utilized
 S.A. Younis et al. / Advances in Colloid and Interface Science 277 (2020) 102108
for the in vitro and in vivo antitumor efficacy via synergistic photody-
namic/photothermal therapy (PDT and PTT) (e.g., 21.7% photothermal
conversion after 12h). The high antitumor efficiency of 2,5-DhaTph-
based COF may be accounted for by the extended 18 π−π conjugations
of the Tph ligand [48]. It was reported that the conjugated π−π system
facilitated the photothermal effect of 2,5-DhaTph-based COF to increase
the heat conduction and transportation process upon laser irradiation.
Accordingly, the excited π−π* was rapidly transformed into the triplet
state accompanied by the generation of highly reactive oxygen species
(ROS) (1O2). This generation of ROS implies the excellent photodynamic
effect of 2,5-DhaTph-based COF with enhanced cytotoxicity for killing
cancer cells. Likewise, a new functionalized nanoscale Porph-COF
(porphyrin-based COP-PEG) similar to the 2,5-DhaTph based COF
was synthesized via coordination of Tph ligand with
2,5-dimethoxyterephthaldehyde (DMTP). This COF was then further
modified with NH2–PEG-2000–COOH (Fig. 5d) [49]. Remarkably, the
porphyrin-based COP-PEG showed good biocompatibility in-vivo with
enhanced antitumor efficacy (e.g., H22 tumor-bearing mice) via syner-
gistic PDT/PTT with higher photothermal conversion efficiency (34.88%)
than that of 2,5-DhaTph COF (21.7%). A series of 3D Porph-COFs (3D-
TPP and 3D PdTPP) with a diamond-like archiotectures were also
synthesized by the reaction of free- and Pd(II)-5,15-bis(4-
formylphenyl)-10,20-diphenylporphyrin ligands with tetrakis(4-
aminophenyl)methane linker via Suzuki−Miyaura cross-coupling
method [66]. These 3D-TPP and 3D PdTPP Porphyrinic-COFs showed
high antibacterial activity toward Enterococcus faecalis and Pseudomonas
aeruginosa biofilms under visible light (460 -525 nm) irradiation due to
their enhanced photosensitizing activity (e.g., through the generation of
singlet oxygen radicals) needed for oxidative destruction of bacteria cells.
2.2. Metal-organic frameworks (MOFs)
Unlike COFs, MOFs have fascinating hybrid architectures in which
the nucleation and growth mechanisms of the desired topologies are
likely affected by ligand functionalities and/or metal node (referred to
as SBU) coordination numbers [7]. Such identification tasks are thus
very important to control the coordination environments of Porph-
MOF materials due to their effect on the reticular structure of designed
MOFs. This is why there are exploratory synthetic strategies focused on
the discovery and understanding of the majority of complex isoreticular
structures of MOF crystals, including porphyrinic-MOFs [67].
From a historical perspective, interest in the synthesis principles of
MOFs has grown steadily since the discovery of the coordination and
solid-state chemistry of zeolites in the 1990s [68,69]. However, unlike
zeolites, they are not purely inorganic compounds but belong to hybrid
organic-inorganic compounds. In the early 1990s, Hoskins and Robson
set the basis and concept for the MOFs through the construction of a
large ranged microporous crystalline solid using structure-directing
agents [70]. Later, the term, “MOF” was first coined by Yaghi et al. in
1995 for an affinity layered Co(II)-trimesate framework of which poten-
tial was explored in reversible gas storage/sorption activities at room
temperature [71,72]. In 1997, a first 3D MOF prepared by Kitagawa’s
group was reported for significant gas adsorption properties under am-
bient temperatures [73]. This first 3D MOF was structurally formulated
as {[M2(4,4′-bpy)3(NO3)4]·xH2O}n (M = Co, Ni, Zn & bpy = 4,4′-
bipyridyl) with channeling cavities for adsorption of small gas mole-
cules [73]. Based on the concept of isoreticular chemistry proposed in
2002, imidazolate-based frameworks (known as zeolitic-imidazole
frameworks; ZIFs) with isomorphic topology has been developed as a
sub-family of MOF by tetrahedral-coordination of metal ions (such as
Co, Fe, Cu, and Zn) with imidazolate linkers [74,75]. Since then, numer-
ous MOFs (more than 80,000 types) have been synthesized with various
isostructures in typologies and morphologies [13,76].Among the new
MOFs families, multivariate MOFs (MV-MOFs) containing mixed-
ligands have recently been developed as a type of multifunctional sites
for MOFs (MFS-MOFs) with a modular design (e.g., adjustable porosity
11
and designable pillared topology) [63,77]. In this view, numerous
isoreticular MV-MOFs with different topologies and functionalities
(e.g., porosity, stability, and catalytic activity) can be built through an
exchange of metal sites or one of their ligands [13,78].
To date, four types of functionalization strategies have been
established to synthesize MFS–MOFs using: (i) pre-synthetic functional
ligands (e.g., MLs or MPs) possessing multiple functional sites (i.e.,
Porph-MOFs) [79], (ii) PSMs of organic ligands or metal clusters [13],
(iii) immobilization of functional guest molecules (e.g., enzymes, pro-
tein, nanoparticles (NPs), and biomolecules) within the framework
structures [80], and (iv) design of a framework with multi-metal centers
or insertion of organic species or guest molecules with other functional
sites (such as organometallic or MPs ligands)[81,82]. These strategies
led to MFS functionalities that behave either independently or collabo-
ratively based on the synthetic approach and molecular starting compo-
nents. Over the last decade, tremendous progress has been made in
tailoring novel porous MFSs-MOFs with specific characteristics that
can offer great promise to improve MOF performance in numerous in-
terdisciplinary fields [83–85].
Porph-MOFs have only emerged as a promising subclass of MOFs
over the last decade [80]. The Porph-MOF family is formed by combin-
ing basic MOF chemistry and nature-driven biomimetic units through
the interconnection of MPs, functional MLs, and ligands with single/
multi-metal ions or clusters (SBUs). Although Porph-MOF frameworks
are still in their infancy, rapid development has increased their applica-
tions in diverse research fields and industrial sectors [84,86]. As
reviewed in “Biomimicry in metal-organic materials,” the incorporation
of MP-based MOF struts has proven to be an efficient tool to design var-
ious MFS-MOFs with structural ligands for potential use in many
catalytic/biomimetic-based applications [30]. It may reflect the fact
that Porph-MOFs bear electron-rich, bio-safe, and biocompatible supra-
molecular building units with limited side effects in healthy in-vitro cells
and tissues (efficient clearance)[87]. Table 2 summarizes a list of most
published Porph-MOFs and their structural MP ligand centers along
with corresponding catalytic/biomimetic activities. In 2011, a multi-
functional Zn2(ZnTCPP)(DPBDPM) MOF BOP (BOP= bodipy-Porph-
MOF) dark-colored crystal was synthesized by reacting two chromo-
phoric ligands of H4TCPP and dipyridyl boron dipyrromethene
(DPBDPM) with Zn-nodes [88]. The obtained MOF BOP (Fig. 6a) exhib-
ited enhanced optical properties and covered the entire visible region
for potential biosensing applications. The enhanced optical features of
MOF BOP were attributed mainly to effective strut-to-strut emission en-
ergy transfer from DPBDPM (i.e., antenna chromophore) to photoactive
Zn-TCPP (i.e., acceptor porphyrinic strut) with an enhanced π-
conjugation system for photo-conversion. More recently, a PCN-223
MOF (PCN = porous coordination network) composed of H4TCPP li-
gands interconnected with Zr-nodes has also been synthesized via a
solvothermal reaction with enhanced light absorption and fluorescence
intensity (extent of quenching 93%) [33]. As such, the porphyrin units
can be used alone as the main building block or merged with other
photo-active organic struts to generate optical Porph-MOFs [89].The po-
tential of 3D Porph-MOF crystals was also recognized for drug delivery
applications using PCN-22 formed from the coordination of ZrCl4 and
H4TCPP ligand [90]. Remarkably, the PCN-221 (Fig. 6b) exhibited low
cytotoxicity for a classical neuronal PC12 cell line with enhanced perfor-
mance in terms of loading/release methotrexate drug molecules (i.e.,
40% at the stomach of pH 2.0 and 100% at pH 7.4 of the intestine).
3. Fundamentals of porphyrin derivative/isomer structures
3.1. Porphyrin structures and their derivatives
The first synthetic report on molecular porphyrin was published in
1986 [91]. Since then, many synthetic porphyrin isomers with different
functionalities have been organically synthesized and produced world-
wide [92]. Molecular porphyrin is an extremely conjugated skeleton of
 12
Table 2
Representative list for some selected (metallo)porphyrin-MOFs and their catalytic/biomimetic activities. (a) TCPP-based MOFs, (b) TPyP-based MOFs, and (c) customized porphyrin-based MOFs.

r. Porph-MOF MPs ligand Secondary ligand Metallic Catalytic/biomimetic activities Ref.

No. center (OMS)

[a] Porph-MOFs based on TCPP porphyrin (carboxylate ligand)

1 3D MOF1 N/A Mn(II) Photocatalytic assisted cycloaddition of CO2 with epoxides under visible light to [265]
produce cyclic carbonates at 1 bar (100% conversion after 20 min when using 30W×3
lamps). High selectivity for CO2 adsorption (ΔH=32.9kJ/mol).
2 TCPP⊂Im-UiO-66 2-(imidazol-1-yl) Zr(IV) Catalytic conversion of CO2 into cyclic carbonate using allyl glycidyl ether at 1 bar (64 [332]
H4TCPP
terephthalic acid ±5% conversion and 90% selectivity).
CoTCPP MOF N/A Co(II) Electrocatalysis [333]
3 Al-PMOF N/A Al(III) Photocatalysis of water splitting (upon metalation of Zn) [319]
4 PCN-222 N/A Zr(IV) Biomimetic phenol oxidation (upon metalation of Fe) [210]
5 OF-525c (5,10,15,20-tetrakis(4-carboxyphenyl) N/A Zr(IV) N/A [334]
6 MMPF-2,4,5 porphyrin) N/A Co(II), Zn(II) N/A [171,172]
or Cd(II)

S.A. Younis et al. / Advances in Colloid and Interface Science 277 (2020) 102108
7 PCN-221 N/A Zr(IV)/Hf(IV) Cyclohexane oxidation (upon metalation of Fe) [214]
Rh-PMOF-1(Zr) Benzoic acid Rh(III) Photocatalytic reduction of CO2 under visible light using acetonitrile and [262]
triethanolamine (TEOA) as sacrificial agents (TOF 0.34 h−1, 99% selectivity, and 3
reusable cycles)
PCN-223(Fe) Fe(III)-TCPP N/A Zr(IV) Electrochemical catalyst for enhanced oxygen reduction reaction (ORR) with [335]
potential to achieve high H2O/H2O2 selectivity (produce b 6% peroxide)
8 Ir-PMOF-1(Zr) Ir(TCPP)Cl Benzoic acid Zr(IV) [(Zr6 Iridium-TCPP catalytic center promotes O–H insertion with a turnover frequency [336]
(μ3- O)8(OH) (TOF) up to 4260 h−1 (total TON of 875 after 10 runs)
2(H2O)10)2]
9 Ir-PMOF-1(Hf) Ir(TCPP)Cl Benzoic acid Hf(IV) [(Hf6 Enhanced carbenoid insertion reaction into silanes (Si–H) bond (93% yield, TOF 2325 [337]
(μ3- O)8(OH) h-1, and TON 1900) with selectivity order of primary N secondary N tertiary Si-H
2(H2O)10)2]
10 NAFS-1 Co(II)-TCPP Pyridine Cu(II) N/A [338]
11 MIL-141 Ni(II)-TCPP N/A Fe(III) Preferential O2 adsorption over N2 [163]
12 MMPF-6 Fe(III)Cl-TCPP N/A Zr(IV) Biomimetic oxidation of THB “1,2,3- trihydroxy- [176]
benzene” and ABTS “2,2-azinodi(3-ethyl-benzothiazoline)-6-sulfonate”

[b] Porph-MOFs based on TPyP porphyrin (pyridyl ligand)

PdCl2-MOF PVP (modulator) Pd(II) Reduction of PdCl2-MOF by hydrazine followed by hydrogenation produced two [339]
types of Pd-MOF NPs (Pd-MOF and PdH-MOF) for enhanced tumor-targeting
photoacoustic imaging (cancer therapy). Photothermal conversion efficiencies (η)
were calculated to be 44.2% PdH-MOF and 27.7% for Pd-MOF at 808 nm.
Three Porph-MOFs with various topologies Dimethyl-acetamide Zn(II) PSE of metal cluster by Cu(II) produced effective catalyst (Cu⸦2 and Cu⸦3) assisted [340]
[Empirical formula: C56H32N14O28Zn5; (DMA) heterogenous organic reactions (e.g., (a) the enamination of β-ketoester to synthe-
C56H32 O9N8Zn3; and C64H36 O10N8 Zn3] size β-enaminoesters (Yield 87 – 97% after 1h); (b) propargylamine derivative syn-
thesis via A3-coupling reaction (yield 87 – 97% after 10 -12 h); (c) alkyne–azide
cycloaddition reaction [Huisgen cycloadditions] (yield 90 -97%))
15 CuP1S N/A Cu(II) acetate Catalytic oxidation of catechol to ortho-benzoquinone (100% conversion after 6 h in [341]
the presence of H2O2 and 24h when using O2, respectively) that is stable for 3 reuse
cycles.

13 Metalloporphyrin–POM-based hybrid N/A Cd(II) as a Oxidation reaction of alkylbenzene [222]

framework metal center;
(M=Mn3+) (PW12O40)3−
as counter
 ions
14 Pd(II)-porphyrin-based MOF (M=Pd2+) N/A Cd(II) Selective oxidation of styrene [342]

M-TPyP

[c] Porph-MOFs based on other customized porphyrin ligands

16 ZnPO-MOF TCPB Zn(II) Acetyl-transfer reaction [162]
(M=Zn2+) (1,2,4,5-tetrakis
(4-carboxyphenyl)
benzene
17 RPMs Metal-TCPP Zn(II) Epoxidation of styrene, and hydroxylation of cyclohexane [163]
(M=Al3+, Zn2+, Pd2+, Fe3+, Mn3+ complexes

S.A. Younis et al. / Advances in Colloid and Interface Science 277 (2020) 102108
complexes)

M-porphyrin
18 ZJU-18,19, 20 N/A Mn(II) or Cd Selective catalytic oxidation of alkylbenzenes [229]
(II)

19 Mn-Porphyrin MOF rods N/A ln(III) Olefin epoxidation [343]

20 MMPF-1 Isophthalic acid Cu(II) N/A [170]

(continued on next page)

13
 14
Table 2 (continued)

r. Porph-MOF MPs ligand Secondary ligand Metallic Catalytic/biomimetic activities Ref.

No. center (OMS)

21 CuP25 N/A Cu(II) acetate Catalytic oxidation of catechol to ortho-benzoquinone (100% to 9.9% conversion after [341]
24h in the presence of H2O2 and O2, respectively)

5,10,15,20-tetrakis
[2,3,5,6-tetrafluoro-4-(4-pyridylsulfanyl)
phe- nyl]porphyrin (H2

S.A. Younis et al. / Advances in Colloid and Interface Science 277 (2020) 102108
P1)
22 {M(C42H16F10N6)]·C2H7N}n Zn(II) Catalytic oxidation of alkylbenzene with high performance for Co-based MOF (81.4% [344]
23 (dimethylamine = C2H7N) Co(II) conversion) as compared to 20.1% conversion by Zn(II)-based MOF

5,15-(4-pyridyl)-10,20-(pentafluorophenyl)
porphyrin (H2Pp)
 S.A. Younis et al. / Advances in Colloid and Interface Science 277 (2020) 102108 15

Fig. 6. Illustration of chromophore and topological features for Porph-MOF based TCPP ligand: (a) confocal laser scanning microscopy images for illustrating the optical properties of BOP
MOF crystals. Black crystals (no emission) and the “green” and “red” crystals (denote emission ranges). Reprinted from [88]. (b) The 3D structure of Zr- PCN-221 along with (b1) octahedral
and (b2) cubic cages. For interpretation of the references, the reader is referred to the web version of the article [87].

tetrapyrrolic macrocycles composed of four pyrrole rings connected via
methine bridges with orientated pyrrolic nitrogens in the interior of the
macrocyclic cavity. The porphyrin crystal (CSD No. 609953) has a mono-
clinic unit cell (space group P21/c) with an interlayer spacing of 3.355 Å.
The pyrrole macrocycles themselves are planar and coplanar with each
other, while being stacked in a rotated, offset manner. In more complex
porphyrins, the individual macrocycles may experience distortions of
up to a few tenths of Ångstroms in their planarity, and this phenomenon
is called ruffling or doming [21]. Furthermore, the aromatic skeleton of a
porphyrin consists of a (4n + 2) π-conjugation system that provides 18-
π electrons and π–π* shifts [93,94]. As a result, numerous efforts have
involved the synthesis of other macrocycles that qualify as porphyrin-
like chemistry, including the so-called porphyrinoid chromophores
and porphyrin isomers, which have other carbon linkage arrangements
[93,95]. Scheme (1) shows the porphyrin-building organic ligands that
are often used in the engineering of Porphyrinic –based frameworks
[96,97].
Scheme (2) presents the most reported porphyrin macrocycle
structures along with the mean bond distances and angles as well
as their isomer molecules with an N4 coordination site (corrole-(.,.,.,.)).
Porphyrin-like molecules belong to a family of no less than seven
isomers (1-7) (Scheme 2) having an N4-core endowed with a
porphyrin ring-like skeleton and one or two cisoid arene fragments
H Metalation of the porphyrin core (e.g., coordinatively bonded metal
(C C C C) as common features [93]. For example, a porphycene
H ions (d- and f-orbitals) with the N4-coordination sites) is thus another
isomer (1) with a structural relationship to the acenes has an N4-
coordination site but with an elongated cavity because of the two
types of linkages between the pyrrolic subunits (two C2 carbon atoms
and two linear linkages) [93]. Other unusual porphyrin-like derivatives
(8) (referred to as N-confused porphyrins (NCP)) have also been
produced by Furuta and co-workers (1994) from Lindsey-type (or
Rothemund) reactions between aromatic aldehydes and pyrrole mole-
cules [98]. The NCP system has an inverted pyrrole ring, thus offering
a remarkable capacity to create transition metal complexes acting as
tetra-coordinate building units [99]. Other closely related porphyrinoids
including azuliporphyrins (9), benzocarbaporphyrins (10),
pyrazoloporphyrins (11), and 1-aza-21-carba-1H, 23H-porphyrin (12)
derivatives (Scheme 2) were engineered with the ability to form various
organometallic derivatives. Corrole isomer (13), norrole, was synthe-
sized via oxidative ring closure of an N-confused bilane and is
considered to be macrocyclically qualified as a porphyrin-like “neo-con-
fused” system. Benzo-fused neo-confused porphyrin (14) was also re-
ported in 2011 as a porphyrin-like organometallic ligand with high
diatropic and aromatic properties [94].
In nature (Fig. 7a), the supramolecular porphyrin-like structures oc-
curred as metallated forms (referred to as mettaloporphyrin (MPs))
such as heme (Fe2+-porphyrin; Fig. 7a-i), chlorophyll a (Mg2+-porphy-
rin, Fig. 7a-ii), vitamin-B12 (Co2+-porphyrin; Fig. 7a-iii), and Cofactor
F430 (Ni2+-porphyrin; Fig. 7a-iv) [31,100,101]. In biology, the alteration
of the MP metal center plays a crucial role in the functionalities. For in-
stance, Fe2+-porphyrin acts as a cofactor of Cytochrome P450 and the
heme-dependent peroxidase family of enzymes to catalyze the in-vivo
oxidation reactions. In chlorophyll a (a family of green pigments), the
Mg(II) metal center chelated to the hydroporphyrin isomer (2 π-
electrons fewer than that of the original porphyrin molecule) acted as
a critical cofactor in natural photosynthesis (e.g., the source of bio-
energy and molecular oxygen on earth) [31,100]. The Co(II) atom in
the core of the tetrapyrrole in vitamin B12 was seen to serve as a crucial
component of the methionine synthase enzyme and L-methylmalonyl
coenzyme that was needed for the operation of the nervous system
[31,102]. Cofactor F430 (Ni2+-porphyrin) is a methyl-coenzyme M re-
ductase (MCR) used to catalyze methanogenesis (i.e., terminal bio-
metabolic step for bioenergetic engineering) at industrial scale [101].
strategy for developing various possible functional porphyrin deriva-
tives (i.e., MPs) [20,51]. Two metalation pathways are to be considered
during engineering MP-based MOFs: 1) halides connected to metal cen-
ters via axial bonding to satisfy charge neutrality in MPs and 2) cooper-
ative coordinate or covalent bonding between metal ions and a neutral
porphyrin (N4 core)[10,21]. Most MPs monomers have many molecu-
larly interesting features such as high thermal stability (300 - 400°C),
rigid planar geometry, high reactivity with intense electronic absorption
and emission, and a small bandgap between the highest and lowest oc-
cupied molecular orbital energy levels (i.e., HOMO/LUMO bandgap ≈ 2.0
eV) [99,103]. Hence, functionalization strategies for Porph-PCP architec-
tures can be conferred via (i) the choice of porphyrin metal centers
(UMCs) and/or (ii) simple insertion of relevant exocyclic functional moi-
eties to the peripheral porphyrin carbon with a new functionality (i.e.,
carboxyphenyl, pyridyl, and cyanophenyl groups, etc.) [99,104,105].
16 S.A. Younis et al. / Advances in Colloid and Interface Science 277 (2020) 102108
3.2. Coordination chemistry of metalloporphyrins
In the area of materials chemistry, the porphyrin macromolecules
are capable of coordinating with almost all types of metal (d- and f-
block elements) in the periodic table [106]. The nature of coordination
and the type of phorphyrin-metal complexes significantly influenced
on the features of porphyrinic-MOFs/COFs materials (e.g., optical fea-
ture, catalytic activities, molecular rigidity, and kinetic stability). Gener-
ally, most of the porphyrin derivatives can form N-ligated porphyrin
complexes via the construction of σ bonds between ionizable pyrrole
within the N4-core (by deprotonation of one or two NH protons) and
metal cations in the periodic table [107,108]. In addition to the N-
metal σ–bonds with the N4-pyrrole core, tetrapyrrole ligands also
have the capacity to coordinate with metal cations via the construction
of π-bonding complexes [106]. Fundamentally, there are two modes of
π-bonding coordination between porphyrin-like macrocycles and
metal ions: 1) π-coordination to unsaturated or aromatic peripheral
porphyrin substituent (as a potential metal-binding site) and 2) direct
complexation to one or more of the N4-pyrrole subunits [106]. It is
thus important to point out the coordination chemistry of the ionizable
N4 coordination site (pyrrole core “radius 2.0Å”) with d- and f-block el-
ements. Apart from d-block elements, non-metallic and semi-metallic
elements (e.g., boron (Group 13), silicon and tin (Group 14), arsenic
and antimony (Group 15), and tellurium (Group 16)) are also able to co-
ordinate with porphyrin macromolecules [107,109].
Scheme 2. Porphyrin macrocycle with mean bond distances and angles as well as the isomers of porphyrin and porphycene macrocycle molecules with an N4 coordination site (corrole-
(.,.,.,.)).
In brief, the porphyrin core can act as a tetradentate ligand by depro-
tonation of two protons (dianion) which generally coordinate with
metal ions having four coordination number (C.N=4) in a square-
planar geometry [107]. There is also a possibility of forming
metalloporphyrins (MPs) with a higher coordination number of five
(C.N = 5: square-pyramidal geometry) and six (C.N=6: octahedral ge-
ometry), depending on the electronic configuration of the coordinating
metal ion [107]. Generally, square pyramidal (C.N=5) is the most com-
monly adopted geometry with a single axial ligand on the apex. The ste-
ric interactions between the N4 core atoms and axial ligand atoms can
also influence the axial bond lengths [107,110]. The square-pyramidal
geometry (C.N=5) can also allow relatively long distances for M–N
bond than that of square-planar (C.N=4) and octahedral (C.N=6) coor-
dination modes. This is because the displacement of the metal atom out-
of-N4 core plane allows radial expansion of thepyrrole core from the
mean porphyrin N4-plane without demanding high energy (e.g., M-N
bond distances: 1.977 – 2.212 Å with C.N=5) [110]. Porphyrin-like
macrocycles can also coordinate with intermediate-sized elements (e.
g., gallium, aluminum, arsenic, antimony, tin, and indium: covalent ra-
dius (rcov) of 1.22 – 1.43 Å) via the formation of five- or six-coordinate
complexes [109]. It was also noticed that all Ti(III)-based porphyrin
complexes had square-pyramidal geometry with five-coordination
bonds and one axial ligand [111]. It was also reported that the electronic
configuration of periodic elements can significantly influence the bond
distances [112]. For instance, an occupied 3d2x-2y orbital can form long
 S.A. Younis et al. / Advances in Colloid and Interface Science 277 (2020) 102108 17

Fig. 7. Examples of naturally occurring MPs and their synthesis: (a) natural metalloporpyrins (i.e., (i) iron(II)-porphyrin “Heme B in RBCs” for oxygen transportation; (ii) magnesium(II)-
porphyrin “chlorophyll a” for photosynthesis; (iii) cobalt(II)-porphyrin “methylcobalamin (as vitamin B12)” required for nervous system function; (iv) nickel(II)-porphyrin “Cofactor
F430” catalyzes methanogenesis in methanogenic archaea). Reproduced from [31]. (b) Synthetic metalloporphyrins of the (i) first, (ii) second, and (iii) third generations (X = EWG or
bulky group and Y= a halogen atom). Reproduced from [103].

equatorial M-N bonds (e.g., the equatorial M-N bond distances of 1.987 -
19992 Å with Co(II) and 1.958 – 1.982 Å with Co(III)) [110]. Further, the
majority of six-coordinate MPs with octahedral geometry are the first-
row transition metal complexes with two equivalent axial ligands
(e.g., imidazole, pyridine, piperidine, or substituted derivatives) [110].
For more details, the nature of the bonds (π or σ) and orbital overlap be-
tween porphyrin-like macrocycles molecules and metal cations (d- and
f-elements) has been discussed comprehensively elsewhere [106,108–
110,112,113].
3.3. Molecular porphyrin derivative synthesis
Porphyrin-derived organic ligands can be produced experimentally
using one of two main strategies: (i) chemical functionalization of nat-
ural (or synthetic) porphyrin molecules or (ii) a reaction consisting of
a pyrrole intermediate [99,103]. In this case, electrophilic aromatic sub-
stitution on the peripheral arrangement of the porphyrin ring (i.e., ni-
tration [114], halogenation [115], sulfonation [116], formylation [117],
acylation [118]), nucleophilic addition [119] or substitution [120], and
cycloaddition reactions [121]) can result in diverse synthetic forms of
porphyrinic derivative structures [103]. On the basis of the exocyclic
functional structures, three-generation structures of synthetic porphy-
rins isomers have been developed and were classified in 1997 (Fig.
7b) [122]. The first-generation structure is the iron-porphyrinate (i.e.,
[Fe(TPP)]Cl) catalyst (Fig. 7b-I) [123]. A second porphyrin generation
is called meso-phenyl-substituted MP derivatives (Fig. 7b-II) with mul-
tiple electronegative or bulky functional moieties [103]. The introduc-
tion of extra electron-withdrawing groups (EWG; such as halogenated
atoms) in the β-pyrrole sites of the 2nd generation ligand gave rise to
the 3rd generation porphyrins (Fig. 7b-III) with the expectation that
the latter should have enhanced catalytic activity while being more re-
sistant to self-oxidative destruction. However, most of the communica-
tions published since the 2000s have shown poor catalytic yields for the
3rd generation MP catalysts compared to their 2nd generation counter-
parts, especially in homogeneous catalysis [103,124–127].
Currently, an infinite number of MP derivative-based organic ligands
structures are being developed with a very similar N4-coordination ar-
rangement to the true porphyrin moiety. In Scheme 1, we compiled
nearly all the common porphyrin-derived organic ligands used to as-
semble Porph-PCP (Porph-MOFs or Porph-COFs) frameworks
[39,128,129]. In this scheme, the porphyrin substituents chosen for en-
hancing ET effects in the Porph-PCPs were carboxyls (-COOH) (i.e., TCPP,
TCBPP, TDCPP, TmCPP, TCMOPP, TBCPPP, TCPEP, and TDCBPP) and es-
ters (-COOR like TmPP) when using meso-substituted phenylporphyrin
in customized MP-based ligands. This is because the oxygen atoms can
provide easy covalent conjugation to form an A-π-D-π-A (electron
acceptor-π bond transfer-porphyrin electron donor-π bond transfer-
electron acceptor) system [19]. In heterogeneous catalysis, MOF-based
18 S.A. Younis et al. / Advances in Colloid and Interface Science 277 (2020) 102108

catalysts have become more promising catalysts than that of porous
COFs polymers because they offering a higher surface area and higher
densities of catalytic metal active sites (e.g., SBU and UMCs) with
greater stabilities [78,130]. However, the progress in porphyrinic-
MOFs based catalysis is still hindered by the lack of knowledge regard-
ing materials engineering strategies and their influence on crystal struc-
tures and coordination sites, which affect shape-selective catalytic sites
for intrinsic catalytic applications. Therefore, more efforts have been
made in the following sections to provide advanced guidelines for un-
derstanding the challenges related to the controlled design of Porph-
MOFs to promote their catalytic applications.
4. Engineering of porphyrinic-MOF frameworks (Porph-MOFs)
To date, research on porphyrin and related species has been receiv-
ing increased attention, especially in the areas of materials science and
solid-state coordination chemistry. Note that several research works
have been published on the assembly of macrocyclic porphyrins and re-
lated MP derivatives for multiple sophisticated disciplines. However,
porphyrin or MPs have rarely been used as bridging organic blocks in
building porous MOFs or COFs (Table 3). In principle, most of the pub-
lished reviews to date reflect an interest in the generation of a plethora
of chemically robust versatile porphyrins macrocycles via metalation of
N4-macrocycles or peripheral substitutions at the meso- and β-positions
(see Scheme 1) for specific applications (Table 3).
The recent interest in porphyrin-based MOFs/COFs has continuously
grown due to several factors: (1) the high molecular stability of porphy-
rins, (2) their chromophoric nature with an intense and red-shifted
Soret band, [131], (3) the propensity to share π-π stacking and the
high electron-rich 18 π-conjugation of the porphyrin macrocycle
[132], and (4) the unprecedented structural topologies and functionali-
ties achieved by different coordination modes (i.e., saturated and unsat-
urated modes) of porphyrin-based isomer linkers with multi-transition
metal ions [33,57]. Therefore, as the diversities of porphyrin ligands
grow, the directions for integrating Porph-PCP platforms are expected
to grow as well to play promising roles in various applications, e.g., arti-
ficial light-harvesting, molecular electronics and recognition, photo/
electro-catalysis, biomedicine/bioimaging, and sensing devices (Table
3) [34,36,133]. However, it should be noted that the research in this
field is still challenging because of the lack of knowledge about: i)
modular designs of Porph-MOFs using polyoxometalate (POM) or
paddle-wheel SBUs rather than the use of metal salts, ii) control of the
topologies of Porph-MOFs containing tetra-linker coordination sites
(e.g., carboxyl, pyridyl, or cyano) and pillared organic assemblies, and
iii) selective encapsulation of host molecules in Porph-MOFs cages
[21,24,39,54]. In particular, POMs are negatively charged metal-oxide
clusters (oxo-rich surfaces) based on d-block transition metals with
high oxidation states (such as W6+, Mo6+, or V5+) [97]. The physical
and chemical properties of POMs can also be modulated (e.g., in terms
of directions and numbers of coordination sites) by selecting appropri-
ate metal species [134]. As such, POMs represent ideal components to
construct hybrid organic-inorganic materials with highly reactive va-
cant sites for catalysis and pharmaceutics [97]. However, the controlled
growth of metalloporphyrin–POM-based hybrid architectures is ex-
tremely challenging option as the in-situ synthesis methodologies.
This is due to the solubility difference between porphyrin-based organic
ligands (soluble in organic solvent) and POM (or SBU moieties with
water-solubility). Hence, the development of new concepts for control
coordination of porphyrin macrocycles and POMs within MOFs/COFs
frameworks remains one of the most important future endeavors.
Herein, we made a considerable effort to summarize how porphyrin-
MOFs and metalloporphyrin–POM-based hybrids might progress fur-
ther toward optimization in terms of their molecular and crystalline
properties.
4.1. Types of coordination frameworks with porphyrin/metalloporphyrin
(MPs) linkers
The choice of customized porphyrin/MP-related linkers and the
metal ion clusters permit control over the stoichiometry, geometry,
and topology of the designed architecture frameworks [96].
The synthesis of Porph-PCPs (e.g., Porph-MOFs/-COFs) has mainly
been developed by four research teams, including (1) Goldberg and
co-workers [27,29,135–144], (2) Choe’s group [145–156], (3) Suslick
and co-workers [157–161], and (4) Hupp’s group [88,162–167]. How-
ever, most of the prepared Porph-PCP (MOFs or COFs) crystals exhibited

Table 3
Some of the important published works on porphyrin and related MP derivatives.

Sr. year Work Field/area Ref.

no.

1 1999 Porphyrin molecular wires with optimized conjugation [345]

2 2000 Self-assembled metalloporphyrin molecular sieves [346]
3 2001 A review on synthesis of porphyrin macromolecular arrays [347]
4 2004 Electronic interactions and spectroscopic phenomena of conjugated porphyrin macromolecules [348]
5 2005 Porphyrin microporous solid materials [157]
6 2007 The interactions of metalloporphyrins as hosts for fullerenes [349]
7 2009 The structural and functional aspects and applications of dendrimers of porphyrins and phthalocyanines. [350]
8 2010 Handbook of Porphyrin Science, which summarized research on large porphyrin arrays as synthetic mimics for photosynthetic light harvesting antenna. [351]
9 2013 1. Electronic spectra of solid-state porphyrin systems including free-base and metalloporphyrins with simple octaethyl substituents and ring insertions. [352]
2. Historical and personal perspective covering porphyrin assemblies in biological and material systems. [353]
10 2014 1. Recent advances in the strategic design of porphyrin coordination polymers. [97]
2. As part of a themed issue on MOFs, porphyrin research continues to be an active and expanding area of MOF research: “Metalloporphyrin-MOFs [129]
including synthetic approaches and functional applications”
11 2015 1. Recent developments in the synthesis, characterization and applications of porphyrin polymers and organic framework materials, including the rapidly [99]
growing area of MOFs and related COFs.
2. A brief summary of fundamental properties of the surface chemistry of porphyrins, phthalocyanines, and their metal complexes, with a particular focus [354]
on the chemical reactions at solid/vacuum interfaces.
12 2016 Highlighting porphyrin-based MOF (Porph-MOF) catalysts in oxidation reactions. [24]
13 2017 Highlighting how the crystallographic topology of porphyrin macrocycles and the inter-porphyrin covalent bonding present in multi-porphyrins influence [21]
the semiconducting properties.
14 2018 1. Application of porphyrin biomolecule-embedded MOFs for optical and sensing applications [287]
2. Utilization of metallo-N4-macrocycles (e.g., porphyrin and phthalocyanine derivatives) as alternatives to Pt-based catalysis in fuel cells. [22]
3. The photosensitizing features of porphyrins macrocycles in imaging technologies (e.g., theranostic applications). [355]
4. Synthesis of conjugation based porphyrin-Cu64 as chelates in positron emission tomography (PET) tracers against diseases or disorders. [356]
15 2019 1. Integration of porphyrin and phthalocyanine (as tetrapyrrole macrocycle) in the synthesis of functional 2D COFs and mesoporous polymers for various [39]
heterogenous catalysis applications.
2. Self-assembly strategies for porphyrin-based functional polymers and their challenges. [128]
 S.A. Younis et al. / Advances in Colloid and Interface Science 277 (2020) 102108
pores filled with relocated solvent molecules [129]. For instance, the Cd
(II) SBUs in a Pd-Py-porph framework (Py-porph =1,10,15,20 tetra-4-
pyridyl-21H,23H-porphyrin) were axially coordinated by two water
molecules and nitrate ions to complete the coordination environment
of the octahedral Cd(II) mode [168]. Only a few of these crystals demon-
strated higher ability to maintain structural integrity upon solvent re-
moval, while most of them do not. For example, axial coordination of
UMCs of TPyP ligand (UMCs = Co(II) or Mn(II)) within its Porph-MOF
framework with two adjoining pyridyl groups led to the creation of a
supportive structure possessing large cavities to improve stability (Fig.
8b) [169]. However, such coordinative saturation of the UMCs reduced
the MP catalytic activities, which thus made porph-PCPs unfavorable
for applications in catalysis, solar cells, and biomedical fields [34,129].
There are at least four major families of porphyrinic-MOF frame-
works, including (1) the pioneering porphyrin Illinois zeolite analog
(PIZA) [157], (2) the metal/metalloporphyrin framework (MMPF) fam-
ily [170–173], (3) porphyrin pillared frameworks (PPF) [147,174], and
(4) robust porphyrin materials (RPM) [163,167]. These prepared
porphyrinic-PCPs materials are customarily built from imino-(pyridyl)
and carboxy-substituted phenylporphyrin derivatives with both SBUs
or POMs to improve the catalytic activities and the rigidity/stability
[51,103,147]. Based on this approach, four PIZA porphyrinic-based
frameworks are constructed by solvothermal coordination of meso-
tetra(4-carboxyphenyl)porphyrin (referred to as T(p-CO2)PP or
H4TCPP) with different metal centers [103]. During synthesis, in-situ
metalation of T(p-CO2)PP macrocycles by metal ions (e.g., Co(III)) was
performed first, and then metallated Co-T(p-CO2)PP was coordinated
with SBU/POM tri-nuclear linear clusters of Co(III), Mn(III), or Zn(II)
ions to build PIZA frameworks [157]. Although PIZA-1 [CoT(p-CO2)
PPCo1.5] (Fig. 9a) was the first reported framework within the PIZA fam-
ily [159], the first practical catalytic study was performed using micro-
porous PIZA-3 towards oxidation of linear and cyclic alkanes and
epoxidation of olefins [157]. PIZA-3 has an isostructural morphology
compared to PIZA-2 (a bent Co(II) SBU) but with a bent Mn (III) SBU co-
ordination. Interestingly, heterogeneous catalysis took place only on the
exterior of the PIZA-3 catalyst due to the constrained diffusion of reac-
tant molecules through its microporous channels. In this case, the inter-
nal cavities could selectively adsorb small and hydrophilic molecules
only, leading to a lack of substrate selectivity. Hence, the solid PIZA-3
was a non-selective active catalyst (Fig. 9b) in all processes catalyzed in-
cluding (1) the epoxidation of cyclic alkenes (Fig. 9b(i–iv)) and (2) ox-
idation/hydroxylation reactions for a mixture of cyclic (Fig. 9b (v-vi))
and linear (or branched) alkanes (Fig. 9b (vii-x)).
Within the MMPF family, these porphyrin-type frameworks have
been widely engineered by Ma and co-workers since 2011 [170–
173,175,176]. Most of MMPF series consists of carboxyphenyl-
substituted MPs (like, TCPP, TDCPP, and DCDBP, in Scheme 2) linked
through different OMSs (e.g., Zn, Cd, Cu, Co, Zr, and Fe metal ions) with-
out any added linkers or spacers [76,177]. For example, the 3D MMPFs
framework was first proposed in 1991 based on palladium (pd2+) Py-
porph units interconnected via octahedral cadmium (Cd2+) ions, as
shown in Fig. (8a) [168]. Two types of connections are formed within
this 3D framework, including a trans coordination of each Cd(II) to
two Pd-Py-porphs to form linear Pd-Py-porph chains and binding of
the two Cd(II) atoms of each Pd-Py-porph to another ring in cis mode.
Furthermore, MMPF-3 and MMPF-6 catalysts have been constructed
by self–assembly methods for catalytic oxidation processes. In this re-
spect, MMPF-3 with permanent porosity was synthesized by
solvothermal coordination between 5,15-bis(3,5-dicarboxyphenyl)-
10,20-bis(2,6-dibromophenyl)porphyrine (dcdbp) and Co(NO3)2
[175]. The fabricated MMPF-3-type frameworks (Co(II)-dcdbp) showed
polyhedral cages based on the 12 vertices of the SBUs formula [Co2(μ2 -
H2O)(H2O)4 (COO)4]. Catalytic results of MMPF-3 crystals (fcu-MOF-1
space group) demonstrated high effectiveness for epoxidation of
trans-stilbene at 60 °C [i.e., yield (87%) and selectivity (96%)] [178]. In
contrast, MMPF-6 (csq, (4,8)-connected topology) has been produced
19
from the in-situ interlinkage of Fe(II)-TCPP with Zr6O8(CO2)8(H2O)8
clusters under solvothermal methods at 135 °C for 80 h [176]. MMPF-
6 exhibited biomimetic peroxidase-like activity, resembling heme-
based catalysts during the catalytic oxidation of 2,20-azinodi(3-
ethylbenzothiazoline)-6-sulfonate (ABTS) and 1,2,3-
trihydroxybenzene (THB) in buffer solutions. Interestingly, catalytic re-
sults of MMPF-6 reflected fast initial catalytic rates of 8.18×10-4 and
1.39 ×10-3 mM/s for ABTS and THB, respectively, with good stability
(10 reusable cycles) [176,179].
The RPM family (M1M2-RPM) is considered to be a second-
generation Porph-MOFs with a paddlewheel structure. The metal acro-
nym in the nomenclature M1M2-RPM is related to the central metals
(UMCs) of the metallated porphyrin ring (M1), whereas the other M2
metal corresponds to the secondary dipyridyl pillar (M2) building
units [24,103]. For example, ZnZn-RPM MOF has been synthesized by
solvothermal assisted coordination between the Zn(II)-TCPP ligand
and a Zn(II)-(dipyridyl)porphyrinate pillar ligand. Subsequently, post-
synthetic modification of the ZnZn-RPM MOF was carried out to pro-
duce Zn(Zn1-xAlx)-RPM MOF catalyst via exchange of dipyridyl-
porphyrin pillars (Zn(II) with Al(III)-dipyridyl porphyrinate) via a
solvent-assisted linker exchange (SALE) method for several days
[167]. Interestingly, the produced ZnAl-RPM isostructure offered high
catalytic efficiency in the ring opening reaction of styrene epoxides
(60% conversion) by trimethylsilylazide (TMSN3) as compared to the
parent ZnZn-RPM MOF (2% conversion) [167]. The high efficacy of
ZnAl-RPM MOF is consistent with the existence of strong Lewis acid
metal sites (e.g., Al(III)) within the MOF structure [180].
Additional isostructural RPM MOFs carrying other free M2 bases (e.g.,
Zn , Co3+, Mn2+, and Sn4+) have also been constructed using the same
2+
Zn(II)-TCPP porphyrin ligand [163]. For instance, the ZnMn-RPM MOF
type prepared by liquid-phase epitaxial growth efficiently catalyzed
the epoxidation of methoxy-styrene [181]. More recently, other RPM
MOFs (i.e., the fluorinated trimetal-porphyrin framework (FTPF) series)
were prepared from M-TPyP (M=Cu2+) porphyrin ligands pillared by
metallated-pentafluoride (NbOF5)2- (M= Fe, Zn, and Ni)) using
solvothermal conditions for the chemical fixation of CO2 and epoxides
with good reusability [182]. Similarly, the PPF series was custom de-
signed by forming 2D porphyrinic layers involving MPs and
paddlewheel SBUs, which were subsequently interconnected by
dipyridyl pillaring linkers to construct 3D PPF structures [79]. Within
the PPF family, a 2D layered Co-PPF-1 catalyst [Co2(CoTCPP)
∙2H2O∙4.75DMF] was constructed from the coordination of Co(II)-TCPP
with Co(COO)4 paddlewheel clusters via a solvothermal reaction
[183]. The Co-PPF-1 was the parent catalyst in the PPF series. However,
it was reported that the catalytic performances of Co-PPF-1 exhibited
lower conversion of trans-stilbene to the epoxide (30.1% selectivity
and 23.7% yield) [173,184]. This was attributed to a reduction in the
number of active sites due to non-controlled alignment of Co-
porphyrin sites within the center of the MOF channels or to their paral-
lel orientation to channels [103]. Using a controlled crystal engineering
strategy, vertically aligned [100]-oriented PPF-11 films of (Zn-TCPP)
2,2′-dimethyl-4,4′- bipyridine attached to ZnO−fluorine-doped tin
oxide (PPF-11/ZnO−FTO) made by a continuous solvothermal method
were reported to display 2−375 times higher photovoltaic efficiency
(power conversion ~0.86%) than that of traditionally visible responsive
Ru(bpy)2+3 -MOFs [185].
Recent studies in the field of COFs have also shown that increases in
molecular complexity by interlinking of the peripheral moieties of the
porphyrins (building units) with organic linkages (See Table 1) can en-
hance their features for modern applications (e.g., catalysis, optoelec-
tronic capacity, and biological compatibilities) [39,49,57]. The
properties and application features of porphyrinic-COFs can be alter-
nated based on the nature of the organic linkages. For example, TAPP
(or Tph) porphyrin ligands were used to synthesize several types of
porph-COFs for different types of potential applications by changing
the organic linkers. In this respect, four Porph-COF nets were
20 S.A. Younis et al. / Advances in Colloid and Interface Science 277 (2020) 102108

Fig. 8. Perspective view of MMPF networks using tetra(4-pyridyl)porphyrin as customized ligands like (a) the Pd-based MP ligand interconnected by cadmium (II) as OMS (insert a
representation of the extended 3D framework) and (b) the first stable Co(II) and Mn(II) MP-based MOFs (MMPF). Reproduced from [129].

constructed through interlinking of the amine functionalities of TAPP
with either 2,5- (dimethoxy)- or (dihydroxy)-terephthalaldehyde
linkers [186] or 2,3- cross-linker isomers [56] via a condensation pro-
cess. Interestingly, both acidic (phenolic) and basic (porphyrin) sites
in the hydroxyl-containing Porph-COFs led to improved crystallinity,
catalytic activities, and stabilities relative to their methoxy analogs.
This was attributed to the intramolecular hydrogen bonding between
two neighboring OH groups of linkers, which stabilized the imine link-
age with a TAPP ligand, leading to an increase in Porph-COF crystallinity
and porosity. Among Porph-COF nets for environmental and energy-
related reactions, two imine-linked Porph-COFs, referred to as COF-
366 and COF-367, were also developed by a direct coupling reaction of
metallated TAPP [Co(II)-TAPP] with terephthalaldehyde and biphenyl-
4,4’-dicarbaldehyde linkages (Fig. 10), respectively, to effectively reduce
CO2 into CO in water under electrochemical conditions [52]. Likewise,
another series of Porph-COFs (the so-called porphyrin-based PAF-40s;
Fig. 10) was developed by covalently bonding M(II) -TAPP [M = H, Fe
& Mn] with aromatic linkages (e.g., biphenyl-4,4’-dicarbaldehyde) via
 S.A. Younis et al. / Advances in Colloid and Interface Science 277 (2020) 102108 21

Fig. 9. Molecular diagrams of the topology of PIZA family and their catalytic activities: (a) the PIZA-1 topology and (b) oxidation reactions catalyzed by PIZA-3 networks (viewed along the
a-axis). Reproduced (adapted) from [103,129].

a one-pot direct coupling procedure [187,188]. These PAF-40s mate-
rials showed noticeable performance in gas storage and catalysis-
assisted alkyne hydration and alcohol oxidation with enhanced selec-
tivity for C2 and C3 hydrocarbons over methane (CH4). Like the TAPP
ligand, four forms of Ni/Porph-COF materials were reported through
covalent coordination linkages of Ni-based tetra[cyanophenyl]por-
phyrin (TCP) ligands with a variety of ethynylphenyl linkers via
alkyne–alkyne homocoupling, Sonogashira–Hagihara coupling, or
alkyne trimerization reactions (Fig. 11) [39,189]. These Ni/Porph-
COF polymers showed significant adsorption selectivity for CO2/N2
with enhanced performances relative to H2 and CH4 gases. In sharp
contrast to these works, it is suggested that Porph-COF properties
such as crystallinity, crystal size, and pore parameters, as well as
their application performance can be controlled and optimized by
considering the nature of linkages and metallated UMCs within por-
phyrin macromolecules.
22 S.A. Younis et al. / Advances in Colloid and Interface Science 277 (2020) 102108

Fig. 10. Synthesis of imine-linked COFs (COF-366 & 367) containing cobalt porphyrins for catalytic CO2 reduction in water and PAF-40 COFs with high C2 and C3 gas adsorption selectivity
over CH4. Reproduced from [39].

Fig. 11. Multiple reaction pathways with Ni-TCP-based MP ligand to form a variety of cross-linked COF polymers. Reproduced from [99].
 S.A. Younis et al. / Advances in Colloid and Interface Science 277 (2020) 102108
4.2. Influence of porphyrins and secondary building unit (SBU) types on
crystal geometry
The open database of the Reticular Chemistry Structure Resource
(RCSR: http://rcsr.anu.edu.au/) for MOF nets includes names, examples,
symbols, and keywords for topologies, polyhedra, and layered struc-
tures; it was published by Yaghi and his group in 2008 to promote a reg-
ulated terminology for different categories of frameworks [190]. The
RCSR database is focused on “the chemistry of stitching molecular build-
ing units by strong bonds into extended structures” and is intended to
help understand the properties of crystalline coordination frameworks
[79,103]. As a new field apart from RCSR, research on ligands and nets
has now focused on the clusters that frame the MOF scaffold (i.e.,
SBUs). Of the porphyrins or MP molecules that adopt a planar
macrocycle configuration, there exists a sub-category of coordination
geometry and symmetry based on ligand stereochemistry of OMS active
sites (Table 4) [191]. Therefore, three to 66 points of extension can be
developed by binding the SBUs to the porphyrinic functional moieties
depending on: (i) unsaturated coordination points, (ii) the type and
number of metal ions coordinated by μ-oxo in the SBU cluster, and
(iii) metal ions that form cluster saturation by axial-coordination li-
gands [103,192–194]. Herein, we present and discuss work related to
the effect of metalation on Porph-MOF architecture dimensions and to-
pologies based on commonly employed tetra-arylporphyrin derivatives
(e.g., TPyP and TCPP seen in Fig. 2) with pyridyl and carboxyl linkers.
Table 4
Stereochemistry of the metal atom symmetry and topology in MPs. [191].
Sr. No. Coordination Number Oxidation state of the open central atom
1 4 2 Square planar
2 5 2,3,4,5
3 6 trans 4,5,6
4 6 cis 4 Trigonal prism
5 7 cis 5 Capped trigonal prism
6 8cis/8bis 3,4
7 8cis/8bis 3,4
a
The geometries and symmetries are only approximate.
b
No example of coordination number 7 with a capped octahedral geometry (C3v) is known.
c
No examples of coordination number 8 with the geometry of a bicapped trigonal prism (C2v, C3v) are known.
d
"N" and "X" denote the isoindole-nitrogen and an axial ligand, respectively.
23
4.2.1. Tetrakis(4-carboxyphenyl)porphyrin (TCPP)-based coordination
frameworks
Since its introduction in 1996 by Goldberg’s group, TCPP has been
one of most frequently studied carboxylate-based porphyrin ligands in
the synthesis of diverse Porph-MOFs [29,177]. Generally, TCPP-based
Porph-MOF topologies are directed by the geometries of the metal clus-
ters, which possess SBUs (i.e., [(M+n )x(COO–)y]z networks) equivalent
to those detected in traditional MOF-based carboxylate ligands (e.g.,
benzene dicarboxylic acid and trimesic acid) [195,196]. Specifically,
carboxylate-bearing TCPP (TCPP-COO–) containing two donor μ3-O
atoms can be categorized as a hard base [29]. In this respect, TCPP car-
boxylate linkers involve electrostatic coordination with either hard or
soft Lewis acidic metal ions to form node-based SBUs with binding en-
ergies around 120–250 kJ/mol. Thus, organizations of diverse oriented
TCPP- MOF crystals can produce many framework geometries through
a reasonable selection of metal clusters because SBU nodes can confer
a specific richness to the recognized open porous TCPP-based MOF
crystals [177].
4.2.1.1. Soft Lewis acid SBUs. As a fundamental rule, the diversified char-
acter of the constructed soft nodes produced via the connection of TCPP-
COO– (hard base) to soft transition metal ions (e.g., Cu2+, Zn2+, Mn3+ /
2+
, Co3+/ 2+, Cd2+, and Ni2) can significantly change the performance of
TCPP-based MOFs in applications [177]. To date, series of TCPP-based
MOFs have been reported in many works [177,197–201]. The first
Coordination geometryb,c Topologyd Symmetrya
D4h
Square pyramidal C2v
Octahedral Oh
D3h
C2v
Cube Oh
Square antiprism D4d
24 S.A. Younis et al. / Advances in Colloid and Interface Science 277 (2020) 102108
example of a TCPP-based MOF [{Zn[Zn(TCPP)]}n MOF] with an approx-
imate tetrahedral geometry was reported by Goldberg and co-workers
through coordination of Zn(TCPP) and zinc acetate (Zn(OAc)2; as a car-
boxylate dimer) SBU under solvothermal conditions in a methanol/eth-
ylene glycol solution mixture [202]. In this case, interactions of Zn2+
ions with the carboxylate moieties of Zn(TCPP) occurred via η1-
coordination to form open exo-cyclic bridging with a tetrahedral
Zn2+-carboxylate [Zn(TCPP)] cluster. Each Zn2+ node was coordinated
to four different Zn(TCPP)-based MP ligands in which only two COO-
on each Zn(TCPP) coordination were deprotonated, as shown in Fig.
(12a). Subsequent changes in the UMCs (e.g., from Zn2+ to Pd2+or
Pt2+ within M2+(TCPP)) led to the creation of isostructural {Zn[M
(TCPP)]}n-based MOFs with different topologies [141]. These
isostructural topologies displayed tiny localized voids rather than
open hexagonal channels in the interpenetrated 3D pts architecture of
{Zn[Zn(TCPP)]}n MOFs (via solvothermal reaction of Zn-TCPP with Zn
clusters). These voids were attributed to the alteration of coordination
symmetry around the fully deprotonated “carbonylic”- O sites of the
Zn-TCPP- ligand (e.g., the four TCPP-COO- moieties). In this regard, the
Zn-based UMC of Zn[Zn(TCPP)] MOF showed a square-pyramidal ge-
ometry with five-coordination (N4-core and pyridine axial ligand),
whereas tetrahedral Zn nodes are four-coordinate, each of which bind
with two TCPP-COO- units and two H2O molecules. As opposed to Zn-
TCPP, different coordination behaviors were seen from the reaction of
deprotonated carboxylate moieties (COO-) of Pt-TCPP and Pd-TCPP li-
gands with Zn clusters. In this case, each Zn node is only coordinated
with two COO- moieties, each of which is from a different M2+(TCPP)
molecule (M2+= Pt or Pd) (COO-…Zn…-OOC). As such, two H2O mole-
cules reacted as auxiliary ligands in the unoccupied coordination sites of
the tetrahedral Zn SBUs (Fig. 12b). Note that the direct coordination of
the TCPP-COO- moieties to four separate Zn nodes should lead to a cyclic
environment with an open 3D polymeric array that is isomorphous to
parent Zn[Zn(TCPP)] MOFs.
M(TCPP)-based MOFs can also be developed through metal-
carboxylate trimers (e.g., ruffled Co3+(TCPP) coordinated in 3-D to lin-
ear forms of PIZA-1, See Fig. 9a), wherein three auxiliary metal cations
Fig. 12. The TCPP-based MP building blocks and related views of the independent (a) 3-D pts framework of {Zn[Zn(TCPP)]}n MOF; (b) {Zn[M(TCPP)]}n MOF isostructural (M=Pd2+or
Pt2+); (c) 3-D Ni2+(TCPP) MOF and related Ni3(COO)6(OH)2(H2O)6 cluster SBUs. (d) PPF series: PPF-3 (Co-based SBU), PPF-4 (Zn-based SBU), and PPF-5 (Pd-based SBU), using the
solvothermal reaction in DMF/ethanol. Reproduced (adapted) from [23,79,129,141,183,203].
are interconnected by TCPP-COO- groups [23]. In these cluster-types,
adjacent trinuclear SBUs of Co2+octahedral nodes are connected by
two μ2-COO- and μ2-H2O ligands (as corner-sharing V-polyhedra
type). Additional axial coordination with pyridine solvent and non-
bridging COO- moieties are also linked to the outer Co2+ nodes to com-
plete the coordination spheres [23]. Thus, two classes with preferably
large pore [atom to atom distances] channels of 18 × 6 and 13 × 6 Å
were apparent in the PIZA-1 framework. Similar to PIZA-1, PIZA-2 has
the same Co3+(TCPP)-based MP ligand, but these MP building blocks
are connected via bent, trinuclear Co2+ clusters that are comparable to
linear, trinuclear SBUs located in PIZA-1 [103,157]. Analogous to PIZA-
1, the 3D Ni2+(TCPP)MOF (pace group PI, triclinic) was prepared
using a linear, tri-nuclear SBU constructed by the solvothermal reaction
of TCPP and Ni2(NO3)2 in a 1:1 H2O/ethanol mixture [203]. The resulting
porous 3D Ni2+(TCPP) MOF structure consisted of 4-connected square-
planar TCPP porphyrin moieties with a linear nickel SBU cluster [Ni3
(COO)6(OH)2(H2O)6], which can accommodate 6-coordinated sites
(O3-O8) per SBU cluster after removing labile bound water (Fig. 12 c).
In this cluster, two carboxylate moieties and hydroxyl groups should
form μ2-bridges between the center and outer Ni2+ ions, while the
other four COO- moieties are coordinated in an ɳ1-fashion (two on the
middle Ni2+ ion and one each on the outer metal ions). Moreover, six
H2O molecules (O20,O30, O40) are also axially coordinated to complete
the coordination spheres of Ni2+-oxo clusters [23].
In the PPF MOFs series, the well-constructed M2(COO)4 metal (M =
Co, Zn, Pd) paddlewheel SBUs were connected to TCPP-based MPs
linkers in the 2D polymeric layers [146,147,204]. Subsequently, sterically
controlled dipyridyl pillar molecules (e.g., 2,2’-dimethyl-bipyridine)
were incorporated as a third component within the framework to prefer-
entially coordinate to the UMCs within the TCPP core (as paddle-wheel
metal sites) and to form 3D paddlewheel-to-paddlewheel stacking pat-
terns [129]. Accordingly, two metal sites (i.e., M(TCPP) UMC site and
paddlewheel SBUs) that were free at the axial junction were able to
form via three probable pillar union schemes including (i) homogenous
AA (paddlewheel-to-paddlewheel), (ii) heterogeneous AB (porphyrin-
to-paddlewheel), and (iii) heterogeneous and homogenous ABBA
 S.A. Younis et al. / Advances in Colloid and Interface Science 277 (2020) 102108 25

(porphyrin-to-porphyrin-to-paddlewheel) connection types (cf. details
in Section 5.3.3) [79,183]. Meanwhile, various metal ions coordinated
in the TCPP core can occur in distinct stacking sequences of 2D TCPP-
based MP layers based on the coordination features of incorporated
metal cations, as seen in Fig. (12d) [129]. For example, Co+, Zn2+, and
Pd2+ can lead to six-, five-, and four-coordinate nodes with octahedral,
tetrahedral, and square-planar geometries, respectively, in their coordi-
nation environment.
4.2.1.2. Hard Lewis acid SBUs. Engineered metal clusters with harder
Lewis acidic metals (such as Al3+, Fe3+, Zr4+, and Hf4+) have attracted
growing research attention with the goal of developing permanently
stable TCPP-based MOFs for energy and environmental applications
[51,177,205]. For example, the high (Z/r) charge density of ZrIV nodes
strongly polarize the oxygen of TCPP-COO- moieties to afford extraordi-
nary chemical stability Zr–O linkages with a notable covalent-link char-
acter [205,206]. Several Zr-based SBUs (e.g., Zr3, Zr4, Zr5, Zr6, Zr8, Zr10,
and Zr18 ) have been developed in cluster chemistry. Only two discrete
In Zr6O8 cluster SBUs, the octahedral cluster of Zr6(μ3-O)4(μ3-OH)4
is the most popular for Zr-SBUs (a square-antiprismatic geometry). In
this architecture, the Zr(IV) center coordinates with six vertices of the
octahedron, while eight triangular faces are alternatively capped by
four μ3-OH and four μ3-O carboxylate groups [205]. Upon thermal acti-
vation at high temperature, the Zr6(μ3-O)4(μ3-OH)4 cluster is
dehydroxylated and loses two μ3-OH groups, which reduces the Zr–O
coordination numbers from 12 to six and distorts the Zr6(μ3-O)6 cluster
by altering the symmetry from Td to D3d (Fig. 13b) [205]. Depending
upon the Zr(IV) coordination geometries (Fig. 13c), different topologies
for Zr(TCPP)-MOFs can be constructed with various performances. For
instance, in the PCN-223 MOF (shp topology), two types of μ4-O coordi-
nation spheres in the Zr6 clusters “Zr6O4(μ3-OH)4(COO)12” (1 & 2) are
shown with similar cores coordinated by 12 μ3-O of TCPP-COO- anions.
These form a Zr6 octahedron with different symmetries (Oh and D4h)
since the triangular faces could be capped by μ3-O or μ3-OH groups
[208]. From a topological view, the Oh symmetry of Zr6(μ3-O)4(μ3-OH)
4(COO)12 may include many symmetry subgroups [205]. In this regard,

Zr-SBUs (e.g., Zr6O8 and Zr8O6) have been widely studied (Fig. 13a) 10-connected (3) [Zr6(μ3-O)4(μ3-OH)4(COO)10]2+(Fig. 13c) coordina-
[205,207]. tion is formed in the DUT-69 MOF by using the 2,5-

Fig. 13. Schematics of Zr6 and Zr8 based SBU clusters and their distorted topologies in various Zr-MOF materials: [a] Observed Zr-based clusters/cores: (I) Zr6O8, (II) Zr8O6, (III) ZrO6, (IV)
ZrO7, and (V) ZrO8. [b] (i) Dehydroxylation of the Zr6(μ3-O)4(μ3-OH)4 cluster to a distorted Zr6(μ3-O)6 cluster upon thermal treatment in a vacuum, and stick and ball representations of (ii)
the perfect Zr6 octahedron and (iii) a squeezed Zr6 octahedron. [c] The formed SBU-based Zr6(μ3-O)4(μ3-OH)4 clusters in Zr-MOFs: 12-connected Zr6 in (1) UiO-66 and (2) PCN-223, (3) 10-
connected Zr6 in DUT-69, (4) 8-connected Zr6 in PCN-222, (5) distorted 8-connected Zr6 in PCN-225, and 6-connected Zr6 in (6) PCN-224 and (7) PCN-777. [d] Various reported topologies
of Zr-MOFs. Reproduced (adapted) from [205].
26 S.A. Younis et al. / Advances in Colloid and Interface Science 277 (2020) 102108
thiophenedicarboxylate (tdc2−) (substituting TCPP) as an organic ligand
in the presence of acetic acid as a modulator [209].
When Zr6 SBU created an 8-connected Zr6(μ3-OH)8(OH)8(COO)2
cluster (4) (Fig. 13c) as in PCN-222 (Porph-MOFs), the symmetry was
reduced from the ideal Oh to its subgroup D4h. In this geometry, the 8-
edges of the Zr6 octahedral cluster are filled by TCPP-COO- moieties,
while the terminal -OH groups of water molecules are connected to
the remaining 8-sites of Zr(IV) coordination centers in the equatorial
plane [210]. For instance, the distorted polyhedron 8-connected Zr6
SBU cluster with D2d symmetry (5) (Fig. 13c) was reported in PCN-
225 [211]. In this case, the triangular faces of Zr6 were capped by eight
μ3-O to form a sqc topology. Furthermore, in PCN-224 (Co), a 6-
connected Zr6 trigonal SBU (D3d symmetry) was found in the crystal lat-
tice [Zr6(μ3-O)4(μ3-OH)4(OH)6(H2O)6(TCPP)1.5 ], forming a hexagonal
planar cluster (6) (Fig. 13c) and she topology [212]. Another 6-
connected trigonal prismatic of the Zr6(μ3-O)4(μ3-OH)4(OH)6(H2O)6
(TATB)2 coordination sphere in PCN-777 (7) (Fig. 13c) was also ob-
served when TCPP was replaced with a relatively large ligand (e.g.,
4,4’,4’-s-triazine-2,4,6-triyl benzoate (TATB)) [213]. Remarkably, it
was speculated that switching the locations of coordinated COO- moie-
ties and axial OH/H2O molecules in the Zr6 clusters could be used for in-
terconversion between a hexagonal planar geometry in PCN-224 and a
trigonal prismatic geometry in PCN-777 frameworks [205].
In Zr8O6 cubic clusters, a distorted octahedral coordination sphere
is formed via coordination of each Zr atom with six μ4-O atoms (three
from COO- moieties and three capped by μ4-O atoms) [205]. For exam-
ple, a cubic Zr8(μ4-O)6 cluster like Zr8(μ4-O)6(OH)8(TCPP)3 (Fig. 13a-II)
was found in PCN-221 [214]. Interestingly, a comparison of the two
clusters of Zr8 and Zr6 structures showed that the exchange of Zr and
μ4-O atoms locations in a Zr8(μ4-O)6 yielded a similar cluster to that of
the Zr6(μ3-O)4(μ3-OH)4 cluster. Each edge of the Zr8(μ4-O)6 SBU was
bridged by one COO- linker from a fully deprotonated TCPP4- ligand in
the PCN-221 MOF to form a Zr8(μ4-O)6(OH)8(COO)12 SBU with Oh sym-
metry. In comparison, each Zr8 cluster was coordinatively connected by
12 μ3-O of COO- anions of the TCPP ligand to form a 3D network; thus,
exchange in the positions of Zr- and O-atoms in the Zr8(μ4-O)6 core re-
sulted in a distortion of the Zr6 octahedron [Zr6(μ3-O)4(μ3-OH)4] coordi-
nation environment [205,207].
Some Zr(TCPP) SBUs with structural diversity are presented in Fig.
(13d) for guiding the topological design of Zr(TCPP)-based MOF
Fig. 14. The TCPP-based MP building blocks and related views of the Fe(TCPP)-MOFs structures with SBUs of Fe(III) octahedra, diiron(II) paddle wheel dimers, and extended [Fe(III)(OH)
O4]n chains. Reproduced from [216].
frameworks [205]. Clearly, the Porph-MOF topology depends upon the
accurate choice of both organic ligands and SBU building units. In this
regard, frameworks with csq, scu, or ftw topologies can be assembled
using tetratopic ligands (i.e., TCPP in PCN-228, 229, and 230) that are
square-shaped with a Zr6 cluster [215]. To combine the versatility of
the MP-based TCPP carboxylate linker and the stability of the Zr
(TCPP)-based MOFs, other stable (M)TCPP-based Zr/Porph-MOFs series
(M= Fe3+, Al3+, Ti4+ or Hf3+ ions) have been designed with different
topologies and functionalities on the basis of TCPP metal centers. For ex-
ample, a series of 3D heme-like iron-porphyrin [Fe(TCPP)] Zr/Porph-
MOF, designated as Zr6-PCN-222(Fe) and Zr6-PCN-223(Fe), have been
prepared with different topologies and catalytic activities [177,210].
Notably, the coordination sphere around the octahedral Zr6 cluster in
(Fe)TCPP-based Zr6-PCN-222(Fe), [Zr6(μ3-OH)8(OH)8(TCPP)2], could
be tuned to form Oh symmetry by adjusting the synthetic reaction con-
ditions [205]. However, the architecture network in PCN-223 contains
uniform, triangular 12 Å 1D channels delimited by three Zr6 SBUs and
three TCPP ligands [208]. This framework prompted the growth of the
first model of the shp-a network in TCPP-based MOFs with remarkably
high connectivity and stability in aqueous solvents at a wide pH range.
Based on the above concept of networking, a series of Fe(TCPP)-based
MOFs were prepared by the solvothermal reaction between iron(IIII)
chloride (FeCl3·6H2O) and TCPP in the presence of various bases
[216], which promoted the formation of metal ion clusters. Depending
on the synthetic conditions, four microporous crystal Fe(TCPP)-based
MOF structures (presenting pts, pcu-b, and fry topologies with three in-
organic SBUs of Fe(III) octahedra, diiron(II) paddlewheel dimers, or ex-
tended [Fe(III)(OH)O4]n chains) can be controllably prepared (Fig. 14).
In this sense, the control synthesis with the introduction of OH groups
could lead to improvements in the Zr6 core hardness and further in-
creases the bonding of the bridging ligands and the Zr6 units, which ex-
hibit exceptional stability toward acid.
4.2.2. Tetra(4-pyridyl)porphyrin (TPyP)-based coordination frameworks
Among pyridinic porphyrins, H2(TPyP) (Scheme 1), a tetra-dentate
ligand is commonly used for engineering chemically stable coordination
frameworks with different coordination geometries (e.g., 2 to 4- coordi-
nate) and topologies (e.g., linear, T-shaped, and square-planar pat-
terned or other less common symmetries) [29,34,79,177].
Fundamentally, the first open porous framework based on a H2(TPyP)
 S.A. Younis et al. / Advances in Colloid and Interface Science 277 (2020) 102108 27

ligand was reported in 1994 by Robson’s group through inter-
coordination with copper [CuI tetrahedral connectors] to yield a 3-D ar-
chitecture with a PtS net topology [217]. The CuI- TPyP architecture ex-
hibited high thermal stability (up to 300 °C), resulting from the
formation of strong nitrogen-Cu bonds within the layered networks
[29]. Since then, a series of 2D and 3D M-TPyP polymeric frameworks
of various topologies and porosities have been prepared via a
solvothermal self-assembly method by utilizing many metal ions (e.g.,
M = MnII, ZnII, CoII, FeII, or SnIV) as useful exocyclic linkers (see Fig.
15a) [30,136,218].
More specifically, a 3D Porph-MOF of [Zn2(H2O)4SnIV(TPyP)(HCOO)
2 ]·4NO 3·DMF·4H2O was prepared from the coordination of
tetradentate tin(IV)−TPyP [SnIV(OH)2TPyP] ligand with Zn(II) ions in
a DMF/CH2Cl2 solution mixture at 50°C for five days [219]. During the
reaction, each SnIV-TPyP unit was bridged first with four Zn nodes to af-
ford porous 2D lamellae (ab-plane) followed by the coordination be-
tween Zn metal formates and SnIV centers in the TPyP cores to
produce a 3D framework (Fig. 15b). Two other MMPF-M (M= Mn(II)
or Co(II)) frameworks were also synthesized from the coordination of
TPyP ligands with either MnCl2∙4H2O or CoCl2∙6H2O under hydrother-
mal conditions (7 days at 150°C). Interestingly, the obtained 3D
{[(MnTPyP)]·H2O}n and1D [(CoTPyP)]n exhibited similar open basic
pyridine groups but with different topologies [30,197]. Crystallographic
results revealed the existence of different topology structures for both
MMPFs due to the change of coordination spheres of the SBU metal-
types (e.g., five- to six-coordination for MMPF-based Co and Mn SBUs,
respectively). The 3D net of the MMPF-Mn displayed an nbo topology
with a rhombohedral space group of R-3M and large open hexagonal
channels (17 × 20 Å) due to the trans-μ1,3 coordination mode of the
Mn-TPyP unit (bond lengths: Mn–N 2.10 Å) and octahedral geometry
of Mn UMCs. In contrast, MMPF-Co exhibited a 1D distorted crystal
(thermoclinic P21/c space group) with single zigzag architecture due to
the linkage of Co UMC to one of the pyridyl arms of a neighboring Co-
TPyP (Co–N bond distance of ~ 1.98 Å). The N-atom of the pyridine be-
longs to the consecutive unit that occupies the fifth coordination posi-
tion with a Co–N distance of ~2.16 Å [30]. Likewise, the spontaneous
liquid-liquid diffusion reaction of a TPyP ligand with diverse metal
salts (e.g., HgI2, Ba(SCN)2∙3H2O, AgPF6, CrI3, UO2Cl2, Th(NO3)4∙5H2O,
and Ce(NO3)4∙6H2O) (Scheme 3) was shown to produce 2D – 3D
metallamacrocyclic coordination networks with different geometries
and topologies (e.g., sql, fsc, and mog) [34]. Interestingly, such struc-
tural diversity was related to the effect of the counterion on space-
filling and iconicity of the M-TPyP-based crystal lattice, which subse-
quently influenced the size and rigidity of the framework.
With the recent advent of new synthesis strategies, POMs were
utilized for the controlled synthesis of functionalized Porph-MOF

Fig. 15. M-TPyP networking geometries (1, 2, and 3D). (a) 2D networking of the M-TPyP motifs with (i) direct inter-porphyrin coordination through M-TPyP cores (yielding a paddlewheel
like pattern) and (ii) the aid of exocyclic metal (SBU). Reproduced from [29]. (b) The 3D lamellar network of ZnII atoms linking SnIV-TPyP porphyrin units along the c axis (on the left: a side
view (II) of the 3D network of the lamellae along the b axis). Reproduced from [219].
28 S.A. Younis et al. / Advances in Colloid and Interface Science 277 (2020) 102108
catalysts due to the high reactivity of abundant oxygen donors on
the surface [10,134]. Further coordination bonding of porphyrin-
based ligands with POM clusters (referred to as Lacunary POMs or
metal-organic polyhedron (MOP)) also provided advantages for
controlled engineering of Porph-MOFs catalysts as compared to the
use of inorganic metal nodes [134]. In fact, the synthesis of MOP (a
discrete metal-organic molecular assembly) can be used as host
molecules to provide tailorable internal volume into Porph-MOF
cavities in terms of metrics, functionality, and active metal sites
[220]. In 1999, an improved approach was proposed for the first
time to construct a 3D coordination framework of Cu-TPyP–POM
[Cu(TPyP)Cu 2 Mo 3 O11 ] using a one-pot hydrothermal reaction of
MoO 3 , copper nitrate, and TPyP ligand at 200 °C [221]. These
authors also prepared a cubic 3D cationic iron-porphyrin framework
[{Fe(TPyP)} 3 Fe(Mo6 O 19 ) 2 ]·xH2 O architecture in which ([Fe 4
(TPyP)3]4n+
n ) was embedded by (Mo6O19)2− cluster anions to reflect
the crystal structure of Cu-TPyP–POM. The results verified that the
produced Cu(TPyP) crystal structure consisted of a tessellated Cu-
TPyP network linked through bimetallic {Cu2Mo3O11} oxide chains
(as a POM water-soluble cluster) into a covalently connected 3D
framework [97]. The large cavities in the iron-porphyrin cubes are
alternately populated by {Mo6O19}2− clusters and disordered water
molecules. Although the construction of (TPyP)POM-based coordi-
nation networks was successful in one step, it is still extremely
Scheme 3. Spontaneous liquid-liquid reaction of TPyP ligand with various metal salts at room temperature to produce crystalline framework materials (TCN =1,1,2,2-
tetrachloroethane) [34].
difficult to control the synthetic reaction of Cu-TPyP–POM frame-
work because of the difference in solubility between reactant com-
ponents. To overcome this difficulty, a two-step preparation
strategy was developed [222]. In this strategy, the traditional
water-soluble POM oxo-rich anions were first replaced by zwitter-
ionic POM complex [{[MnIII(DMF)2TPyP](PW12O40)}2−; termed as
Lacunary POM (or MOP)] through the reaction of water-soluble
H3PW12O40 with organic soluble MnIIICl-TpyP (metalloporphyrin)
in DMF. A layered hybrid framework of a {[Cd(DMF)2 MnI II(DMF)
2TPyP](PW1 2O40)}·2DMF·5H 2O was then successfully constructed
upon the solvothermal reaction of the zwitterionic complex with
Cd(NO3 )2·4H2 O in DMF and acetic acid for 48 h at 80 oC. Based on
this approach, another novel thermo-responsive framework,
HMOF-1 solid (hinged MOF-1), displaying a 3D “lattice fence” topol-
ogy with extraordinary thermal enlargement and shrinkage behav-
iors was reported by Choe and co-workers through the assembly of
H2TPyP and CdI2 [150].
4.2.3. Other customized metalloporphyrin-based coordination frameworks
Among the documented porphyrinic frameworks, a tetra-
carboxyporphyrin ligand named H4TCPEP [5,10,15,20- tetrakis(4-
carboxyphenyl)ethynylporphyrinate] was designed by Matsunaga and
co-workers and contained an acetylene group between the peripheral
C-atom at the meso-position and the 4-carboxyphenyl group [223].
 S.A. Younis et al. / Advances in Colloid and Interface Science 277 (2020) 102108 29

Using TCPEP ligand, a 3D Porph-MOF network {[Zn4(μ3-OH)2(H2O)2
(ZnTCPEP-H)2(DABCO)]·2DMF·10.5H2O} (Zn4·ZnTCPEP·DABCO) was
constructed by coordination of ZnTCPEP-H with tetra-nuclear Zn(II)
cluster nodes{Zn4(μ3-OH)2(H2O)2} and DABCO (Diaz-abicyclo[2.2.2]oc-
tane) (Fig. 16a) [223]. Another rare indium (InIII)-based Porph-MOF
net with the pts topology (named MMPF-8) was also created by the
reaction of custom-designed 5,10,15,20-tetrakis(4-carboxybiphenyl)
porphyrin (TCBPP) and InIII ions under a solvothermal reaction in
DMF at 85 °C for 48 h [224] (Fig. 16b). PCN-230 with Zr6-containing
isoreticular Porph-MOFs with a ftw-a topology was prepared through
the solvothermal reaction of Zr(IV) ions with TCP ligand in DMF for
12 h at 120°C (Fig. 16c) [225]. There was also an effort to construct
2D sql frameworks (Fig. 16d) in a nitrobenzene–benzene solvent mix-
ture using Cu(T3MTPP) or Zn(T3MTPP) (T3MTPP= 5,10,15,20-tetrakis
[3,4,5-tris(methylthio)phenyl]porphyrin) and BiBr3 as nodes [226].
However, solvent elimination from this network resulted in
crystallinity loss due to the formation of mixed chelating and bridging
disposition between the thioether groups of T3MTPP and Bi2 units;
thus, Br- anions and nitrobenzene molecules occupied the remainder
of the Bi3+ coordination spheres [23]. Moreover, paddlewheel PPF-6
and PPF-225 were synthesized using dicarboxyphenylporphyrin li-
gands such as cis- and trans-H4DCPP (5,10-di(4-carboxyphenyl)-
15,20-diphenylporphyrin and 5,15-di(4-carboxyphenyl)-10,20-
diphenylporphyrin), respectively [145,154]. In this regard, the PPF-6,
[(Co(cis- ZnDCPP)(4,4′-bpy)]·4DMF·H2O, with a CdI2-type kgd 2D to-
pology was synthesized from the solvothermal reaction of Zn(cis-
DCPP) with cobalt ions in the presence of a 4,4′-bpy spacer in DMF sol-
vent (Fig. 16e) [145]. Meanwhile, a paddlewheel (PPF-25) framework
with T-shaped geometry and anatase (ant) topology was self-
assembled using paddlewheel ZnII SBUs and mixed linkers of 4,4′-bpy
and Zn (trans-DCPP) via a solvothermal reaction in a mixture of
DMF/ethanol solvents (Fig. 16f) [79,154].

Fig. 16. Representative topologies of some Porph-MOFs families: (a) 3D extended structure of Zn4·ZnTCPEP·DABCO along the ab-plane. (b) Structure of MMPF-8. (c) Structure of PCN-230
constructed with Zr6 clusters and H4TCP [79]. (d) Zn(T3MTPP)-based MPs and a single sheet of the 2D sql net of {BiBr3[Zn(T3MTPP)]}n (right side) [226]. (e) 1D tape motif assembled from
cobalt paddlewheels and cis-ZnDCPP for PPF-6. (f) 2D porphyrinic (4,4) grids assembled from trans-DCPP for PPF-25 [79].
30 S.A. Younis et al. / Advances in Colloid and Interface Science 277 (2020) 102108
Fig. 17. Coordination of customized TImP porphyrin ligand in NJNU-1 framework: (a) Chemical structure of customized H2TImp ligand and (b) 2D lamellar network of NJNU-1and the
coordination mode of TImP and Fe3+. Reproduced from [79,227].
NJNU-1 (NJNU= Nanjing Normal University) is another highly sta-
ble Porph-MOF in air and alkaline solvents; it is prepared by coordina-
tion of customized imidazolyl-porphyrin (tImp) building units with
Fe3+ ions (Fig. 17) [227]. The higher stability of NJNU-1, especially in
NaOH solution (∼27.5 M), was explained by the strong Fe–N bonds be-
tween imidazolate moieties and the high-valence SBUs (e.g., Fe3+, a
harder Lewis acid as discussed above). Other substituted porphyrins
containing multiple peripheral linkers with more than four carboxylic
or pyridyl moieties with the capacity to coordinate with more metal
centers (i.e., 4 -7 metal nodes) were also developed and used for the
preparation of porous Porph-PCP frameworks. In this respect, custom-
designed octatopic porphyrin building blocks of TDCPP and TDPAP
(Scheme 1) [i.e., TDCPP= tetrakis(3,5-biscarboxyl-phenyl)porphyrin;
TDPAP= tetrakis(4,4-dipyridylamino-phenylene)porphyrin] have
been utilized to design three porous isostructures (ZJU-18, ZJU-19, and
ZJU-20: ZJU= Zhejiang University) of Porph-MOF frameworks
[97,173,228]. These isostructure-based diverse SBUs were synthesized
by a solvothermal method from a mixture of M-TDCPP (M = MnIIICl
or NiII) and MnCl2 or CdCl2 in a mixed solvent of DMF and acetic acid.
The RCSR of the prepared isostructures (ZJU-18, ZJU-19, and ZJU-20) ex-
hibited 3-periodic, binodal, and edge-transitive nets with a tbo configu-
ration [229].
5. Diverse synthetic strategies for porphyrinic-coordination
frameworks
Given the diversified constituents and tailorable topologies of syn-
thesized porphyrinic-based framework crystals, control of their molec-
ular architectures is critical to understand the topological visualization
of particular crystals with distinct and functional properties.
5.1. Synthetic approaches of (inorganic) SBU clusters
Molecular SBU clusters of Porph-MOF frameworks usually consist of
polynuclear metal units formed in-situ by sequential self-assembly
(SSA) of the mononuclear metal cations from their metal salts during
a one-pot synthesis of the MOF molecules [230]. Despite the outstand-
ing progress made through this easy synthetic scenario, other advanced
‘out-of-the-box” approaches have been employed to create ideal topol-
ogies of multifunctional Porph-MOF networks via ex-situ preparation of
0-periodical MOP [M2(carboxylate)4] followed by coordination with
porphyrin ligands [17,231]. The MOP nodes are commonly pre-
synthesized as soluble discrete polynuclear complexes via the coordina-
tion of metal salts with monocarboxylate alkyl/aromatic ligands (such
as acetate, formate, benzoate, pivalate) (Fig. 18a) [230,232]. The MOP
unit can thus provide exceptional functionalized nodes to improve the
crystalline stability and porosity (large channels) at the supramolecular
level to serve applications in various fields [232,233]. Therefore, synthe-
sis of a functional MOPs could be utilized as modular units (i.e., starting
supramolecular building blocks, SBBs) to build crystalline MFS-MOF
molecules with a well-defined coordination geometry and symmetry
in the inner-coordination sphere [234,235].
Smart control over architectures is critical when using highly con-
nected polyhedral SBB clusters because they can be further functional-
ized either on the vertices or on faces to create MFS-MOF crystals [17].
For example, using the SBB approach, 12-, 18-, or 24-connected MOPs
can be applied for the synthesis of frameworks with gea, fcu , and rht-
type topologies, respectively [17,236,237]. Principally, MOP-based SBU
modules can be used to control the synthesis of the framework struc-
tures (e.g., predicting topologies and porosity) or to provide additional
functional features to the solid-state porous Porphyrin-based frame-
work materials [232,238,239]. However, it should be noted that such a
two-stage route of POM-based porphyrin framework synthesis is
time-consuming relative to a simple self-assembly method that relies
completely on one-pot self-assembly reactions. In other cases, use of
the multi-component clusters of polynuclear SBU complexes (or
MOPs, as functional sites) in the preparation of heterometallic SBU-
based Porph-MOFs (MFSs-MOFs) can rarely yield phase-pure porous
crystals of known chemical composition. Thus, in an attempt to explain
MOP or polynuclear SBU chemistry, the types of self-assembly of poly-
nuclear metallic clusters of SBUs are classified into four categories ac-
cording to the coordinative sphere of their metal nuclei (Details in
Table 5). More information on the types of SBUs clusters could inspire
those who attempt to assemble modular and non-interpenetrating
Porph-MOF networks with robust structures and permanent porosity.
SBUs consisting of more than one metal ion interconnected through
μ-oxo and carboxylate or pyridine scaffolds can be connected to the or-
ganic linkers from three to 66 points of extension. These extension
points are based upon the number of: (i) metal ions forming the cluster,
(ii) unsaturated coordination sites, and (iii) metal atoms saturated only
by the ligands building the cluster [103]. For example, a 2D porous (Cu)
TPyP-based Porph-MOF framework [Cu2(OAc)4{Cu(TPyP)}1/2] was
formed by the reaction of H2TPyP as an axial ligand for binuclear [Cu2
(OAc)4] Cu2(OAc)4] units in a benzyl alcohol medium [240]. CZJ-1
(CZJ= Chemistry Department of Zhejiang University) with cubic α-Po
topology was another porous Porph-MOF, which contained a [Zn2
(MnOH-TCPP)(L´): L´= N,N´-di(4-pyridyl)-1,4,5,8-
naphthalenetetracarboxydiimide] unit [17,228]. In this Porph-MOF
type, paddlewheel nodes of Zn2(COO)4 are bridged by MnOH–TCPP in
2D sheets, which are further bridged with pillared spacer L´ organic moi-
eties to form a 3D porous structure.
In the development of trinuclear SBU approaches, other progress
was achieved by using the oxo-centered trimeric mixed metal acetates
[Fe2M(μ3-O)(AcO)6: M= Co2+, Ni2+, or Mg2+], for example, in the
 S.A. Younis et al. / Advances in Colloid and Interface Science 277 (2020) 102108 31

Fig. 18. Possible structure directions of various SBU metal clusters and their connecting modes in MOF frameworks: (a) Structure extension of (from top to down): {M2(CO2)4}{Li2M2(CO2)
-
6},{Zr6O8(CO2)12}, {M3O(CO2)6}, and {Zn4O(CO2)6}) SBU clusters. (b) Four connecting modes of the [Fe2M(μ3-O)] cluster (COO and terminal acetates are represented in black and purple,
respectively). Reproduced from [230].

scalable design of mixed-metal MFS-MOF frameworks [241]. In other
cases, the produced trinuclear nodes (M = Fe, Cr, Al, Sc, V, and In)
serve as the sources of 4, 5, 6-connected nodes (Fig. 18b)[242]. These se-
ries of trinuclear nodes could also be used for the construction of nu-
merous types of (0D, 1D, 2D, and 3D) Porph-MOF networks via
replacement of AcO anions with various porphyrin-based
polycarboxylate linkers [230,242]. For instance, nanoscopic polyhedral
cages consisting of 5,15-bis(3,5-dicarboxyphenyl)-10,20-bis(2,6-
dibromophenyl)-porphyrin ligands with Co2(μ2-H2O)(H2O)4-(COO)4
molecular units have been developed via solvothermal reactions to
form cubohemioctahedral SBBs [175]. The prepared SBBs then acted as
12-connected nodes in an fcu-MMPF-3 network topology with three
types of interlinked polyhedral cages: a cubohemioctahedron, a trun-
cated tetrahedron, and a truncated octahedron (Fig. 19a-d) [17]. Other
uniform polyhedron SBB-based porphyrins were also produced from
the reaction of self-assembled custom-designed tetra-dicarboxy-por-
phyrins with Zn2+ and Cd2+ cations, which then functioned as molecu-
lar building units [172]. The faces of the porphyrin moieties joined
triangular units of either M2(CO2)3 or M(CO2)3 and allowed the devel-
opment of small cubicuboctahedral SBBs. These SBB units could be
fused to form highly symmetric broadened topology pcu networks, de-
noted as MMPF-4(Zn) and MMPF-5(Cd), which showed two distinct
polyhedral cages with permanent microporosity (Fig. 19e) [17].
In summary, the interplay between the acidity strength of carboxyl-
ate moieties (in the MOP complex) and organic struts (in Porph-MOF)
was important for two main reasons: 1) the acidity profile affects the
relative nucleation growth rates along the crystallographic directions
and 2) the tetrahedron complex cluster affects the degree of remnant
coordination spheres of the Porph-MOF crystal during growth
[243,244]. Furthermore, coordinative saturation of SBU clusters to

Table 5
Types of POM-based SBU clusters classified based on the coordination environment.

Sr. SBUs unit Unit structure Properties/remarks

No.

1 Binuclear [M2(RCO2)4(L)2: M = Cr2+, Mo2+, Cu2+, Co2+, or 1) The simplest polynuclear clusters using monodentate ligand; in some cases, they form dinuclear
(M2) SBUs Zn2+, R=acetates, and L=ligand] paddlewheel building blocks using polydentate linkers.
2) The carboxylate bridges interconnect via syn-syn modes to two metal centers, whereas the
apical axillary L ligands (N- or O-donors) form an octahedron geometry directed around the
plane of the square.
3) The SBU can extend onto Porph-MOF nets in three ways: (i) through axillary coordination
positions with no effect on the SBU core, (ii) connection via bidentate ligands, and (iii) substi-
tution of both RCOO- and L linkers with porphyrinic ligands, which could involve a distorted
coordination sphere.
2 Triangle (M3) [M3O(RCOO)6L3] 1) Octahedral sphere node contains sixth coordination bridging of μ3-O oxo anions with metal
SBUs cations (typically, 3d metals with oxidation states of +2, +3, and in some cases +4).
2) In some cases, octahedron core partially occupied by reactive solvent molecules and extended to
use axillary ligands (i.e., Porphyrin or MPs).
3) Trinuclear SBUs provide a platform for heterometallic [M' M2O(RCOO)6L3] complexes to ratio-
nally design heterometallic Porph-MOFs (MFSs-MOFs).
3 Tetrahedron [M4O(RCOO)6] 1) The central μ4-O2– oxo-anion collectively connects four M(II) cations in a tetrahedron order
(M4) SBUs (e.g., Zn(II)acetate [Zn4O(AcO)6]) to form a scaffold-like primitive framework of cubic topology.
2) Each pair of M(II) cations is connected by carboxylate (COO-) anions to form the edges of the
tetrahedron structure via a syn-syn mode.
4 Hexanuclear [M6O4(OH)4(RCOO)12] (e.g., M = 1) Hexanuclear units of coordinative high valence metal cations like 3d (e.g., Zr, Ti, and Cr) and
(M6) SBUs Zr6-oxo-hydroxocarboxylate) lanthanide elements (Ln) with organic ligand to form M-oxo-carboxylate cluster.
2) The most commonly used are Zr6 clusters.
32 S.A. Younis et al. / Advances in Colloid and Interface Science 277 (2020) 102108
sustain Porph-MOF crystalline structures is still one of the main chal-
lenges for catalysis applications because of a lack of free accessible
metal active sites for catalytic reactions. Hence, the use of
metalloporphyrins (e.g., MPs with UMCs metal centers) peripherally
connected to SBU building blocks for Porph-MOF construction is a better
choice to address the obstacle of saturated SBUs in catalysis [245,246].
This may also be considered as another fundamental challenge within
the synthetic strategies for porous MP-based MOF frameworks
[188,200,247].
5.2. Unsaturated metal center (UMC) sites within porphyrinic-MOF crystals
Metalloligand building units, such as MPs with well-defined UMC
sites, offer potential opportunities to create functionalized MOFs frame-
works with enhanced redox activities for enhanced catalytic applica-
tions [78,248–250]. Generally, the assembly approach for MP-based
MOFs can proceed in two sequential steps: (1) building MPs by
interlinkages of metal cations (frequently 3d metal ions) with a free-
base porphyrin ligand and then (2) coordination of the MP ancillary
linkers with SBU units containing OMSs similar to or different from
UMC-types of MP ligands [65,199,251–255]. During the SSA processes,
the functional ancillary groups of MPs metalloligands can take part in
the self-assembly of SBU by coordinating a secondary metal cation
through weak interactions like intermolecular H-bonds. Free-base por-
phyrin ligands are almost inexhaustible sources for constructing either
H-bonded or M–L-driven UMC-based homo- or hetero-metallic Porph-
MOF frameworks [17].
For instance, MMPF-6 is synthesized from the interlinkage of the Fe-
TCPP–Cl ligand and Zr6O8(CO2)8(H2O)8 SBU cluster to produce a hexag-
onal and triangular 1D channel framework (Fig. 20a) [176]. Four other
MP-based MOFs with 3D nets are as follows: [(CH3)2NH2]-[Cd2-
(HCOO)2(Mn-TCPP)], [Zn2(HCOO)2(Mn-TCPP)], [Zn2(HCOO)(Fe-
TCPP)], and [Cd3(H2O)6(μ2-O)(Fe-TCPP)2] (Fig. 20b) [256]. The first
three frameworks are synthesized from the coordination of M´2(COO)4
SBU paddlewheel subunits (i.e., pre-assembled from the reaction of
Fig. 19. The three polyhedral cage types in MMPF-3: (a) cubohemioctahedron, (b) truncated tetrahedron, and (c) truncated octahedron. (d) 3D MMPF-3 network presenting
interconnection of its polyhedral cages. (e) The synthetic schemes of MMPF-4 (M=Zn) and MMPF-5 (M=Cd) based on small cubicuboctahedral SBBs. Reproduced from [17].
metal nitrates (M´ =Zn or Cd) with formate ligands) and a MCl-TCPP
(M = Mn or Fe) bridge in DMF and acetic acid mixed solvent [17]. The
later architecture is built under similar conditions but by interlinking
of decadentate ligands consisting of μ2-O bridging FeCl-TCPP dimers
with 10 Cd3+ trinuclear cations. The results indicated that coordinated
frameworks with Mn-TCPP yielded isomorphous structures with AB
stacking patterns of the 3 D nets and a tetragonal I4/mmm space
group. Here, the two Fe−TCPP ligands are coupled by a μ2-oxo to form
a dimer with ABCDABCD stacking patterns with Cd cations (tetragonal
I41/acd space) (square-pyramidal geometry with Zn SBU) [256]. The
octatopic porphyrin ligand [5,10,15,20-tetrakis(3,5-biscarboxyl-phe-
nyl)-porphyrinate; TBCPP] was also used to build three isostructures
of UMCs containing Porph-MOFs [i.e., 3-periodical ZJU-18, binodal
ZJU-19, and edge-transitive tbo ZJU-20 networks] with hetero-
metallic metal centers [173,229]. Notably, these frameworks were pro-
duced from the direct solvothermal reaction of Mn(III)Cl–TBCPP with
metal chloride salts of Mn2+ (ZJU-18), Ni2+ (ZJU-19), and Cd2+(ZJU-
20) rather than using pre-assembled SBB clusters in a controlled DMF/
acetic acid solvent mixture at 80 oC for one week [229]. The change in
framework topologies is related to alterations in M-TCPP configurations
from bowl-shaped to flat or wavy patterns [17]. More recently, a 3-D ro-
bust structure PCN-222(Fe) catalyst (a type of MP-based MOFs) was
prepared using the solvothermal method in N, N'-diethylformamide
(DEF) solvent for 24h at 120°C. A PCN-222(Fe) peroxidase-like catalyst
with high chemical stability was synthesized from the direct in-situ co-
ordination of pre-assembled Fe(III)-TCPP-Cl ligand with Zr6 node
(ZrCl4) in the presence of benzoic acid as a modulator [257].
Besides the in-situ engineering of MP-based Porph-MOF frame-
works, external immobilization of MP-bearing Lewis acid functional
sites can be another effective route to control the formation of Porph-
MOFs with UMC active sites. For example, a one-pot procedure was re-
ported to integrate Zr-TCPP ligands into UiO-66(Zr) (UiO = University
of Oslo) as functional guests to form porphyrin-MOF composites with
free UMCs sites [258]. The produced Zr-TCPP@UiO-66(Zr) composite
maintained the original UiO-66 crystal topology and stability in addition
 S.A. Younis et al. / Advances in Colloid and Interface Science 277 (2020) 102108 33

to enhanced catalytic oxidation due to the existence of Zr4+ UMCs ac-
tive sites in the Zr-TCPP functional MP. Nevertheless, the direct immobi-
lization of metalloporphyrins (MPs) within ordinary (non-porphyrinic)
MOF networks during in-situ growth remains a challenge [247]. For in-
stance, a possible deactivation of UMC metal sites of MPs via auxiliary
coordination with ordinary ligands can take place during in-situ growth
of hybrid Porphyrin@MOF (details in Section 6.1). More recently, Co-
TCPP-based MOF(Al) frameworks with enhanced electrochemical sens-
ing of H2O2 were rationally designed to overcome this challenge; this
framework was fabricated on the surface of carbon cloth (Fig. 20 c) by
a two-step evaporation/transformation method under microwave irra-
diation [254]. The pre-synthesized carbon cloth coated with Al2O3 was
immersed into a DMF/H2O solution mixture containing Co-TCPP ligand.
Under microwave radiation, Al2O3 acted as an SBU for uniform crystalli-
zation of Co-TCPP-based MOF(Al) onto carbon cloth at 140°C for 20 min.
The high redox activity of Porph-MOFs contributes to the pre-coating
step of the Al2O3 nodes, which allows uniform growth of Co-TCPP-
based MOF(Al) in a well-aligned interface on carbon cloth. In summary,
MPs cores (free or metallated base) may serve a pivotal role in the syn-
thesis of UMC-based Porph-MOF frameworks by controlling molecular
porphyrin stacking and their coordination modes with secondary SBU
nodes or metal cation building blocks.
5.3. Experimental synthetic aspects of Porph-MOFs
Many synthesis strategies based on either conventional or high-
throughput (HT) approaches have been developed in the field of
MOF design and engineering (Fig. 21) [70,259,260]. Despite the
real diversity, only one-step thermal growth using a standard solvo
(hydro)thermal method has been widely reported as the most uti-
lized protocol for the synthesis of Porph-MOF crystals
[182,254,261,262]. Conventional solvo(hydro)thermal procedures

Fig. 20. Representative examples for control structure topologies of various Porph-MOFs: (a) View of 3D Zr-MMPF-6: a1) Fe–TCPP Cl MPs, a2) Zr6O8(COO)8(H2O)8 SBU, and a3) hexagonal
and triangular 1D channels of MMPF-6. (b) View of the 3D-Mn-MP-based MMPF (Zn or Cd) frameworks: b1) deprotonated Mn-MP ligand, b2) the coordination environments of M´ SBUs
and Mn-MPs atoms, b3) lamellar network of Mn-MPs linking M´2(COO)4 paddlewheel SBUs, b4) view of the 3D Pp framework. (Color codes: C, gray; O, red; Cl, green; N, blue; Mn, orange;
Zr, turquoise; other M´ SBU, cyan or light-blue square pyramids). (c) The proposed orientation of Co-TCPP-MOF(Al) layer onto the surface of the carbon cloth and its crystalline structure.
Reproduced from [17,176,254,256]
34 S.A. Younis et al. / Advances in Colloid and Interface Science 277 (2020) 102108
mainly proceed via conventional electrical (CE) heating for several
hours or days without any parallelization of the reaction. Such syn-
theses mainly involve two reaction setups: (i) solvo(hydro)thermal
under autogenous pressure and temperature above the boiling point
of the solvent and (ii) non-solvo(hydro)thermal at low temperature
(i.e., direct precipitation at room temperature) or near the boiling
point (i.e., thermal assisted crystallization) of the solvent and ambi-
ent pressure [11,70]. The main advantages of these routes are (1) a
facile one-pot procedure, (2) controlled production of a single crys-
tal topology, (3) in situ synthesis of SBU during the reaction proce-
dure, and (4) high purity and yield [263].
Typically, once a super-saturation environment has been achieved in
thermal-assisted crystallization, the auto-assembly reaction between
the ligand and metal cation or clusters leads to the production of MOF
particles with sizes ranging from tens of nanometers to micrometers
based on the modulator agent used [11]. Therefore, appropriate atten-
tion should be given to certain operation parameters (e.g., temperature,
solvent type, reactant concentrations, time of reaction, and reaction pH)
Fig. 21. Summary of synthetic strategies for tuning the crystal growth of metal-organic frameworks. In the scheme center: evaluation of growth mechanism as a function of ΔG free energy
change, kinetic curves with the change of radius r of nucleus and supersaturation levels.
during synthesis to maintain the integrity and functionality of the reac-
tive building units for the proper building of the coordination bonds
[78,237,256]. For instance, the operational levels of these parameters
are fundamentally adjusted depending upon the nature and type of
building units used.
The reliance on low-temperature (b 140°C) solvo(hydro)thermal
routes is common when growing molecular Porph-MOF crystals since
it is feasible to tune the nucleation rate and crystal growth [264,265].
For example, TCPP-based MOF(Cu) thin films were synthesized via di-
rect reaction of a pre-assembled Cu(OH)2 nano-needle SBU array with
a saturated H2TCPP solution in an H2O/ethanol mixture (at mixing ratios
of 100:0 to 20:80) at room temperature for 12–24 h [193]. At H2O/eth-
anol ratios of 60/40 to 40/60, the Cu(OH)2 needles dissolved during the
solvothermal process to produce Cu2+ ions, which acted as an SBU for
coordination with the H2TCPP linker to yield insoluble Porph-MOF crys-
tals containing binuclear Cu2(COO)4 paddlewheel SBUs [193]. Changing
solvent ratios was found to alter the crystal morphology of a TCPP-based
MOF(Cu), likely due to the influence of solvent polarity on the solubility
 S.A. Younis et al. / Advances in Colloid and Interface Science 277 (2020) 102108
of TCPP linkers and its proteolysis properties. Two other types of (M)
TCPP-based MOFs [{M4(TCPP)2(DMF)8}n: M= Ba2+ or Sr2+ ions] with
high fluorescence properties and monoclinic P21/c space groups have
also been constructed under analogous solvothermal conditions using
DMF solvent acidified by HCl at 120-100 °C for 3 days [199]. The acidi-
fied condition influenced the coordination environment by assisting
the deprotonation of TCPP ligand to propagate a molecular chain with
Ba/Sr metal cations throughout the crystal lattice.
More recently, two 2D layered catalysts of (M)TCPP-based MOF
(M= Cu or Zn) catalyst were synthesized by modulating solvothermal
reactions between metal nitrate salts and TCPP in the presence of a
polyvinyl-pyrrolidone (PVP) in DMF/ethanol solution mixture at 80 °C
for 20h [266]. Interestingly, the results revealed that the PVP surfactant
acted as a template/cap directing agent to the top faces of the grown lat-
tices to help in the anisotropic growth of 2D grids of Porph-MOF nano-
sheets with a 3 D topology structure via AB stacking rather than bulk
crystals. Surfactant-assisted synthesis is a key regulator for Porph-MOF
crystal formation because of it roles in (1) self-assembly of nanoreactor
micelles that modulate the crystal growth, (2) capping or inhibition to
either reduce the rate of crystal growth and provide steric stabilization
for nanocrystal formation or to induce anisotropic growth of Porph-
MOF faces, and (3) as a molecular template for crystal growth with var-
ious hierarchical porosities (meso-, micro- and/or macropores)
[11,267]. Therefore, utilization of templating agents (such as organic
solvents, surfactants, ionic liquids (ILs), and POM (or MOP; as functional
reactive vacant clusters)) during solvo(hydro)thermal synthesis could
provide a new controlled route to generate analogs of prototypal
Porph-MOFs with new tunable functionality for applications like cataly-
sis [268]. However, it should be noted that the nature of the modulator
plays an important role in either decelerating or facilitating the frame-
work crystallization processes [70,268,269]. This is because the modula-
tor competes with the porphyrin ligands to form coordination bonds
with the SBUs. This, in turn, influences the size and morphology during
nucleation and crystal growth. Accordingly, molar ratios of modulator
agents as well as the metal precursor: organic linker ratio can either in-
hibit or promote the crystal growth rate, even in the more complicated
synthetic methods. Like modulators, other additives (referred to as cap-
ping or molecular blocking agents like pyridine) can also be used either
to terminate or to slow the rate of Porph-MOF crystal growth by inter-
vening in the growth mechanism in a definite direction on certain crys-
tal faces [270].
The contra-diffusion (i.e., liquid phase epitaxy, layer by layer (LBL),
or step-by-step) method is another synthesis strategy intended to
grow MOF crystals with more pronounced film morphologies at the liq-
uid/liquid interface through slow diffusion of the two reactants (i.e., or-
ganic linkers and metal units) containing layers in opposite directions
[271]. The so-called contra-diffusion can be employed using either
two immiscible [272] or partially miscible [273] solvents with a density
difference. Fundamentally, the thickness and size/morphology of the
Porph-MOF frameworks can be easily controlled in this approach by
selecting appropriate synthesis parameters such as temperature, reac-
tion, miscible solvent, and the ratio of reactants in a layered diffusion
system (e.g., use of high reactant ratios to yield N 1 μm film thickness)
(Fig. 21) [11]. For instance, well-defined nanotube structures of
Porph-MOFs (diameters of 60–80 nm and wall thicknesses of about
15–25 nm) have been produced using the contra-diffusion method
[274]. In the method, a chloroform solution containing TPyP-TPyTa
(TPyTa = tris(4-pyridyl)1,3,5-triazine) was slowly diffused into an
aqueous solution of HgCl2 at room temperature for about one week.
Considering the benefits of the diffusion method, we expect to see
growth in this particular research activity for the synthesis of Porph-
MOFs.
As compared to conventional synthesis, HT assisted methods
(e.g., microwave (MW), mechano(sono)chemical or sonochemistry
(ULS), and electrochemical) are powerful synthesis strategies to ac-
celerate systematic reaction rates of Porph-MOF formation with
35
short reaction times (rarely exceeding 1 h). These HT synthesis
methods frequently help in providing a better understanding of re-
action trends and the role of synthetic parameters on the coordina-
tion environment and crystallinity of the framework [70,275].
However, it should be noted that changes in the activation energy
from CE heating (i.e., heat transferred from a hot surface through
convection) to electromagnetic radiation (MW), mechanical waves
(ULS), or electric potential (electrochemistry) energy sources also
have a strong influence on the crystallinity and morphology of the
formed frameworks. This is mainly because of the different amounts
of energy used per molecule in a system for different reaction times
and pressures [70]. Therefore, in these HT procedures, attention
must also be given to the selection of suitable solvents and energy
input [11]. It is expected that the synthesis of Porph-MOFs via the
HT methodology could have significant effects on the characteristics
of crystal lattices (e.g., crystal size and topology). For instance, in
regular MOF synthesis, particle sizes decrease from microns (by
using CE heating or mechanochemical) to nanometers (by using
MW or ULS protocols) [11]. Though the MW- and ULS-assisted strat-
egies enable rapid nanocrystal formation, they do not always allow
fine-tuning of size and structure topologies of the resulting Porph-
MOF. This should be related to the rapid and uniform thermal energy
transfer of MW and ULS irradiation and their influence on the kinet-
ics of crystal formation (i.e., crystal nucleation). Moreover, in elec-
trochemical synthesis, only Porph-MOFs with similar SBUs (for
anodic metal cations) can be synthesized. In some cases, the organic
linker and/or the conducting salt molecules are incorporated into the
MOF pores during crystallization [70,275]. Other reaction variables
such as choice of solvent (e.g., viscosity, vapor pressure, and chemi-
cal reactivity), temperature, or gas atmosphere can play an impor-
tant role during sonochemical and MW syntheses. For instance,
high vapor pressure “volatile” organic liquids are usually not effec-
tive reaction solvents because they reduce the intensity of the
cavitational collapse and negatively influence the overall reaction
pressure and temperature.
To overcome solvent limitations, supercritical synthesis has
recently been developed to effectively construct MOF nanoparti-
cles. The method involves a rapid expansion of fluids (e.g., CO 2
and/or ionic liquids (ILs); Fig. 21) into the supercritical state by
regulating solution pressure and temperature [269]. As a solvent,
supercritical CO 2 (scCO 2 ) and CO 2 -expanded liquid (CXL) in the
subcritical state (critical temperature (304.21 K) and pressure
(73.83 bar)) can be utilized as green chemical solvents for modu-
lating Porph-MOF synthesis [269]. Hence, controlled synthesis of
Porph-MOFs in an IL/scCO 2 /surfactant media provides a highly
promising direct assembly procedure to produce well-defined
shapes of Porph-MOFs with higher crystallinity and porosity
[11,269]. Other unusual solvents like microemulsions (which
maintain the hydrophilic-lipophilic solution balance) act as
nanocontainers and are also employed as a new approach to
gain a certain degree of control over crystal size, shape, and tex-
tural properties of MOFs crystals [11]. Using reverse
microemulsions, the building components are usually dissolved
in both the aqueous (metal ions or SBUs) and hydrophobic (por-
phyrin organic linker) phases [270]. Readers may refer to recently
published works for more details [250], [276],[277],[268], [249],
[11], [275], and [70].
5.4. Practical strategies in the design of porphyrinic MOF crystals
Practically, it is useful to organize different synthesis strategies
for self-assembly of Porph-MOF crystals based on the nature of the
porphyrin linkers and metal salt counter ions (Fig. 22(a–b))
[204,249]. However, the main challenges for Porph-MOF crystalliza-
tion are summarized as: (1) the UMCs inside the core of the porphy-
rin may effectively be saturated by coordination with axial ligands
36 S.A. Younis et al. / Advances in Colloid and Interface Science 277 (2020) 102108
during in-situ coordination and post-synthesis processes and (2) the
unmetalated free-base porphyrin has a tendency to coordinate with
metal cations intended for SBU construction [147]. Therefore, in this
section, we discuss how these challenges are addressed by using the
PPF family as a model for Porph-MOFs synthesis. One of the main
benefits of the PPF series is that one can practice several approaches
to functionalize the Porph-MOFs (e.g., pore size change via bilayered
coordination with UMCs site) without affecting their overall struc-
tural topology [77,204].
Assembly of the PPF series (Table 6) can be simply generated by a
two-step reaction process [13,155]. A distinct feature of the PPF series
is the presence of second pillaring sites, where two organic ligands of
MPs and pillar bipyridyl molecules are interconnected by paddlewheel
metal clusters of [M2(COO)4] SBUs [77,278]. In this family, the
paddlewheel SBUs of the M2(COO)4 metal cluster [M = Zn2+ or Co2+]
allowed the synthesis of a 2D layer via coordination with the four car-
boxyl arms of the M-TCPPs linkers [183]. At this point, the axial sites
along the crystallographic c direction of the SBUs in the 2D layers are
readily available to join second pillar ligands by extending their 3D
framework topology. Notably, the pillars at this stage cannot differenti-
ate between the coordinative sites with metal cations either in the
paddlewheel SBUs or in MPs if they are freely available. Hence, in
most PPF series, the paddlewheel SBUs clusters within 3D PPF frame-
works are fully coordinated by equatorial TCPP carboxylate linkers
and secondary pillars in the axial direction. Bipyridyl pillar molecules
that are used to connect the 2D layers include 4,4′-bipyridine
(BPY), 3,6-di-4-pyridyl-1,2,4,5-tetrazine (DPT), 2,2’-dimethyl-4,4’-
bipyridine (DMBPY), and N, N’-di-(4-pyridyl)-1,4,5,8-
naphthalenetetracarboxydiimide (DPNI)) (see Fig. 22). Therefore, con-
trolled synthesis of PPF is necessary for creating Porph-MOF bearing
UMCs (cf. Section 5.2 for details).
The first stage of the PPF series (2D layers) synthesis process is asso-
ciated with three classes of stacking arrangements, homogenous AA,
heterogeneous AB, and intergrowth of ABBA connection types (i.e.,
combined AA and AB pattern) with a fsx topology (Fig. 22c) [147,204].
These stacking patterns of the 3D pillared PPFs frameworks can be al-
tered by the coordination geometry of the MP metal cations and the na-
ture of bipyridyl pillars [77]. Therefore, structural topology, stacking
fashion, and pore surfaces of the PPF series can be systematically
Fig. 22. Schematic of a Porph-MOF framework assemblage: (A) free-base porphyrin and (B) metalloporphyrin (MPs) linkers and SBU metal nodes. (C) Classification of stacking patterns
developed during pillaring in the PPF series. In the scheme center and bottom: different dipyridyl pillar structures and M-TCPP ligand used in the construction of PPF series with a summary
of PPF structures. Reproduced from [147,204].
controlled by tuning the concentrations and ratios of the three building
units (e.g., M-TCPP, paddlewheel SBUs, and pillar) and the solvothermal
reaction temperature. For example, the 2D sql layer topology of PPF-1
showed a change in the final AB stacked fashion interlayer distance
from 17.49 Å at 120 K to 18.58Å at 296 K during solvothermal coordina-
tion between Zn-TCPP and Zn2(COO)4 paddlewheel SBUs [163]. The 2D
porphyrinic layers are connected together via introducing a dipyridyl
pillaring linker (i.e., bpy) through stacking patterns to yield a final 3D
framework with a fully coordination environment, depending on the
number of free available coordination (i.e., UMC or SBU) sites. Further-
more, as seen in the bottom of Fig. (22), the coordination numbers
and additional binding centers for the secondary pillars in the
paddlewheels and porphyrins can alter the topology features in the
PPF framework. For instance, most PPF series exhibited homogeneous
pillaring (AA) for two paddlewheel M2(COO)4 SBUs, while heteroge-
neous pillaring is only found in the 3D nets of PPF-3, [Co2(CoTCPP)
(bpy)2] (NO3), via an AB stacking pattern of both porphyrin CoII centers
and Co2(COO)4 SBUs [174]. Comparatively, PPF-4, i.e., [Zn2(ZnTCPP)
(bpy)1.5], showed an ABBA stacking sequence with an fsx topology via
connection with the porphyrinic 2D layers [Zn2(ZnTCPP)] [174].
The provision of accessible OMS in Porph-MOF crystals has always
been one of the main research goals in catalysis. In this respect, the con-
trolled insertion of OMS can be achieved via integration and use of MP
paddlewheel SBUs and sterically hindered pillar ligands, which provide
an ideal controllable strategy for incorporation of various metal centers
into the hetero-metallic metallic isoreticular Porph-MOFs. In this re-
spect, the pillaring dipyridyl linkers can provide peculiar binding cen-
ters (UMCs) in the interiors of the PPF family (e.g., 2D PPF-18 and 3D
PPF-20) due to their highly porous in nature. As such, the original topol-
ogy of the PPF MOFs can be adjusted only by replacing pillaring linkers
to develop new isoreticular structures with different properties and
functionalities (Fig. 22) [147,204]. For instance, alteration of the
pillaring ligands from simple to longer pillars in PPF materials can
help in the selective coordination of the axial ligand with the
paddlewheel metals clusters rather than of UMCs (i.e., accessible cata-
lytic sites). This selectivity results from the steric repulsion generated
from the alkyl/aromatic groups in the longer chain bilayers. For in-
stance, alteration of bpy to DMBPY (with two methyl substituted
groups) preferentially creates only AA stacking between paddlewheel-
 S.A. Younis et al. / Advances in Colloid and Interface Science 277 (2020) 102108
to-paddlewheel connections (e.g., PPF-11 series including PPF-11-Zn/
Zn, PPF-11-Co/Co, PPF-11-Mn/Zn, and PPF-11-Fe/Zn) (See Fig. 22)
[17,152,204]. The effect of porphyrin linker symmetry on the PPF frame-
work topology has also been studied during one-pot solvothermal syn-
thesis [145]. Interestingly, a lower porphyrin symmetry (e.g., cis-/ trans-
DCPP) reduces PPF framework topology to C2v symmetry with a defec-
tive paddlewheel structure as compared to that of the D4h when using
the M-TCPP ligand, even when the same assembly conditions are ap-
plied. As an example, the solvothermal synthesis of PPF-6-Zn/Co using
Zn-[cis-DCPP], a paddlewheel Co cluster, and a bpy pillar ligand
proceeded with an AB type of stacking fashion with a CdI2-type kgd
2D topology (i.e., a rare shape form a relatively unusual three-legged
piano stool structure) [145]. On the other hand, 3D PPF- 25 with T-
shaped geometry was developed from the solvothermal coordination
between Zn[trans-DCPP] and octahedral Zn2(COO)4 paddlewheel SBU
pillared axially via a bpy organic pillar. Such a 3D PPF-25 framework ex-
hibited an AB stacking pattern and ant topology [154]. The T-shaped ge-
ometry, unlike the more frequently formed Y-shaped linker, is rarely
observed in Porph-MOF synthesis, and it cannot accommodate the rtl
topology [204,279]. In contrast, the square pyramidal and Y-shaped ge-
ometry were reported in the bilayer topology, and the 3D ABBA stacked
structures are more popular topologies reported in many Porph-MOF
frameworks [79,96,148,204].
Recently, research interest in Porph-MOF functionalization has pop-
ularized porphyrin as a pillared bridging ligand for the development of
new crystals with diverse and intriguing properties. Indeed, rational co-
ordination of porphyrin ligands or modification of their UMC metal sites
has propelled the generation of many series of multi-functional Porph-
MOFs (e.g., MMPF, PPF, PIZA, NJNU, and PCN) with new tunable charac-
teristics [17,30,64,89,197,280,281]. Compared with the pillared PPF
family, recent research interest in Porph-MOF functionalization has
also popularized porphyrin as a pillared bridging ligand to design
POM-based porphyrin zwitterions crystals with diverse and intriguing
properties. The standard solvothermal synthesis and, in some cases,
slow-evaporation/diffusion approaches were the most frequently
applied synthetic methodologies during the serendipitous
discoveries of new functional Porph-MOF networks
[13,86,177,199,249,253,261,262,282,283]. For example, the NJNU series
of 2D Porph-MOFs was constructed by the reaction of hard Lewis acid
metal (M) ions (such as Fe3+, Al3, Zr4+, and Ti4+) with an imidazolyl-
based porphyrin ligand (tImp) under solvothermal conditions [225].
The resulting NJNU series materials had exceptional stability in air and
in a saturated NaOH solution (∼27.5 M) due to strong M–nitrogen
bonds generated by the tImp linker moieties and the high-valence of
the metal nodes [227]. The first example of a tetrazoleyl-porphyrin-
based MOF, the so-called UTSA-57 or {Mn(II)0.5[Mn(II)4Cl(Mn(III)Cl-
ttzpp)2(H2O)4]}·(DEF)20·(CH3OH)18·(H2O)12, was reported by Guo’s
group [284]. The UTSA-57 (UTSA = University of Texas at San Antonio)
was constructed by solvothermal reaction of cubic Mn4Cl(ttz)8-(H2O)4
POM clusters (ttz = tetrazole) with 5,10,15,20-tetrakis[4-(2,3,4,5-
tetrazolyl)phenyl]-porphyrinato-manganese(III)chloride, (Mn(III)Cl-
ttzpp) in methanol/water/DEF mixed solutions. Notably, the M4Cl(ttz)
2+
8-(solv)4 SBU clusters (M = Mn , Fe2+, Cu2+, and Ni2+) are popularly
used POM-based SBUs nodes in the MOF field [177]. Four series of alka-
line earth metal–based 2D and 3D Porph-MOF frameworks, referred to
as Mg(HDCPP)2(DMF)2]n·(H2O)7n, Ca(HDCPP)2(H2O)2]n·(DMF)1.5n,
and [M(DCPP)(H2O)·(DMA): DMA = N,N-dimethylacetamide & M=
Sr2+ or Ba2+]n, were also synthesized using a solvothermal approach
at 120 oC for 3 days [285]. These isomorphic Porph-MOFs bore a periodic
nanosized porosity with a triclinic system P1 space group for Mg2+ and
Ca2+ based Porph-MOF and a monoclinic crystal system with a P21/n
space group Porph-MOFs group based on Sr2+ and Ba2+ SBUs. More-
over, gadolinium-based Porph-MOF has been synthesized via a four
step-solvothermal reaction of TCPP with GdCl3 salts in the presence of
polyetherimide (PEI) and cetyltrimethylammonium bromide (CTAB)
in DMF at 110°C for dual-modality imaging and photodynamic therapy
37
[286]. In this procedure, CTAB was used as a modulator agent, while PET
was a capping layer for further functionalization with folic acid to re-
duce in vivo toxicity. More recently, self-assembled Lacunary POMs con-
taining TPyP pyridyl ligands and Keggin-type trivacant
phosphomolybdate [A-α-PMo9O34]9− was prepared by Suzuki and co-
worker to offers ideal SBB building units with higher stability and reac-
tivity for subsequent MFS-MOF fabrication [134].
6. Custom functionalization of Porph-MOFs and their composites for
emerging applications
In addition to their supramolecular and porous nature, engineering
of Porph-MOF composites via combining or scaffolding them with
other functional elements (See Fig. 1) is an option to induce new prop-
erties that did not exist in the pristine frameworks. These types of
Porph-MOF-based composites have been recently reported to provide
more multifunctional active sites, superior mechanical stability (even
under harsh conditions), electrical conductivity, gas storage, (bio)sens-
ing, (bio)imaging, unique optical properties, and improved catalytic ef-
ficiency [254,286–288]. Herein, the porphyrinic MOF-based guest-host
composites are divided into two main categories based upon synthesis
strategy and nature of the guest molecules. The two categories are: (i)
guest@Porph-MOF systems in which functionalized guest particles are
incorporated within the Porph-MOF networks and (ii) Porph@MOF sys-
tems where porphyrins (as functionalized guests) are encapsulated
within the pristine MOF crystals. Fundamentally, those two types of
composite systems can be synthesized via different strategies including:
(1) in-situ self-assembly (in-situ growth or pre-synthesis) and (2) em-
bedding and thin-film (post-synthesis) methods for core-shell and non-
core-shell type formation, respectively [13,14]. Remarkably, post-
synthetic strategies can allow incorporation/encapsulation of an infinite
number of functionalities of specific interest into the Porph-MOFs while
maintaining the framework integrity, which cannot be achieved via a de
novo direct assembled (solvo(hydro)thermal) approach [289–291].
Table 7 summarizes the frequently reported functionalized Porph-
MOF composites, approaches used for their synthesis, and related appli-
cation/performance.
6.1. Custom-design of composite via pre- and post- synthetic
functionalization strategies
In the pre-synthesis strategy, foreign ‘functional’ guest particles act
as the core in the feedstock cages of the Porph-MOF frameworks
(shell) during their in-situ solvo(hydro)thermal growth to develop
core-shell like composites [14,147]. However, in some cases, the direct
introduction of guest functionality into Porph-MOFs via the pre-
synthesis (i.e., de novo assembly) method is quite challenging. This is
mainly due to factors like limited ligand solubility, chemical and ther-
mal instability of guest molecules in the reaction media, incompatibility
of functional guests with Porph-MOF counterparts, and the undesired
reaction interference between metal ions/porphyrin ligands and guest
functional moieties [261,275]. To address these issues, the LBL assembly
is another approach in which the surface functionalization of the guest
core is carried out to allow the uniform growth of the framework on
the guest core [57]. Under controlled conditions, porphyrin ligand pre-
cursors rapidly coordinate with metallic nodes to form the shell and
build the crystalline Porph-MOF network around the carrier core
guest, as assisted by the interface between guest surfaces and porous
framework functionalities without changing the parent topology
[63,165,289]. Step-by-step assembly has also been suggested and in-
volves specific functionalization of the guest surface to control the
growth of the MOF shell despite the complications involved in this pro-
cess. For example, functionalization of reduced graphene oxide (rGO)
with a pyridine ligand (donor-π-acceptor G-dye) was prepared as a
pre-step for controlled synthesis of a shell of rGO@Fe-Porph-MOF com-
posite with enhanced catalytic activity for oxygen reduction reactions
38 S.A. Younis et al. / Advances in Colloid and Interface Science 277 (2020) 102108

Table 6
List of synthesized porphyrin paddlewheel framework (PPF) materials (produced via solvothermal methods) and their basic characteristics.

Sr. MOF namea Pillaring ligand MP linkers Paddlewheel Stacking Topology Solvothermal Ref.
No. SBUs pattern synthetic strategy

1 2D PPF-1 DPDS Pd-TCPP Zn2(COO)4 -- --- CE heating/DEF-EtOH (10 [357]

Zn2(PdTCPP)(DPDS)2 (4,4'-dipyridyl μLHNO3) (v/v=3:1)
disulfide)
2 PPF-1-Zn/Zn ---- Zn-TCPP Zn2(COO)4 AB Sql CE heating/DEF-water [183]
[(Zn2(ZnTCPP). 3H2O.2DEF)] (v/v=1:1)
3 PPF-1-Co/Co ---- Co-TCPP Co2(COO)4 AB Sql CE heating/DMF-water [183]
[(Co2(CoTCPP). 2H2O.4.75DMF)] (v/v=1:1)
4 PPF-3-Co/Co BPY Co-TCPP Co2(COO)4 AB pcu-b CE heating/DMF-EtOH [174]
[Co2(CoTCPP)(bpy)2](NO3)] (v/v=1:1)
5 PPF-3 Co/Co [checkerboard-like 2D sheet] BPY TCPP Co2(COO)4 AB --- CE heating/DMF-EtOH [358]
[Co2(CoTCPP)(bpy)2](NO3)] (v/v=3:1)
6 PPF-3-Mn/Zn BPY Mn-TCPP Zn2(COO)4 AB pcu-b CE heating/DMF [156]
[Zn2(MnTCPP)(bpy)2](NO3)]
7 PPF-3-Mn/Co BPY Mn-TCPP Co2(COO)4 AB pcu-b CE heating/DMF [156]
[Co2(MnTCPP)(bpy)2](NO3)]
8 PPF-3-Fe/Zn BPY Fe-TCPP Zn2(COO)4 AB pcu-b CE heating/DMF [156]
[Zn2(FeTCPP)(bpy)2](NO3)]
9 PPF-3-Fe/Co BPY Fe-TCPP Co2(COO)4 AB pcu-b CE heating/DMF [156]
[Co2(FeTCPP)(bpy)2](NO3)]
10 PPF-4 BPY Zn-TCPP Zn2(COO)4 ABBA Fsc CE heating/DMF-EtOH [174]
[Zn2(ZnTCPP)(bpy)1.5] (v/v=1:1)
11 PPF-5-Pd/Co BPY Pd-TCPP Co2(COO)4 AA Fsc CE heating/DMF-EtOH [174]
[Co2(PdTCPP)(bpy)] (v/v=1:1)
12 PPF-5-Pt/Co BPY Pt-TCPP Co2(COO)4 AA Fsc CE heating/DMF [156]
[Co2(PtTCPP)(bpy)]
13 PPF-5-Ni/Zn BPY Ni-TCPP Zn2(COO)4 AA Fsc CE heating/DMF [156]
[Zn2(NiTCPP)(bpy)]
14 PPF-5VLO/Zn BPY Zn-OTCPP Zn2(COO)4 AA Fsc CE heating/DMF [156]
[Zn2(V = OTCPP)(bpy)] V=O/Zn
15 PPF-6-Co/Zn BPY cis-[ZnDCPP] Co(NO3) -- Kgd CE heating/DMF- EtOH [145]
[{Co(cis-ZnDCPP)}(bpy)]·4DMF·H2O 2.6H2O (v/v=3:1)
Co2(COO)4
16 PPF-11-Zn/Zn DMBPY Zn-TCPP Zn2(COO)4 AA fsc CE heating/DMF- EtOH [152]
[Zn2(ZnTCPP)(dmbpy)]·1.1DMF·1.2H2O (v/v=3:1)
17 PPF-11-Co/Co DMBPY Co-TCPP Co2(COO)4 AA Fsc CE heating/DMF-EtOH [152]
[Co2(CoTCPP)(dmbpy)]·2.0DMF·0.2EtOH (v/v=3:1)
18 PPF-11-Mn/Zn [Zn2(MnTCPP) DMBPY Mn-TCPP Zn2(COO)4 AA Fsc CE heating/DMF- MeOH [152]
(dmbpy)]·NO3·0.4DMF·0.9H2O (v/v=2:1)
19 PPF-11-Fe/Zn [Zn2(FeTCPP) DMBPY Fe-TCPP Zn2(COO)4 AA Fsc CE heating/DMF-MeOH [152]
(dmbpy)]·NO3·2.6DMF·1.2MeOH (v/v=2:1)
20 PPF-18 DNPI Zn-TCPP Zn2(COO)4 AB Bilayer CE heating/DEF-EtOH (v/v= [148]
[Zn2(ZnTCPP)(DNPI)] 3:1)
21 PPF-19 DNPI Zn-TCPP Zn2(COO)4 AA Fsc CE heating/DMF-EtOH [148]
[Zn2(ZnTCPP)(DNPI)] (v/v=2:3)
22 PPF-20 DNPI Zn-TCPP Zn2(COO)4 ABBA Fsc CE heating/DMF-EtOH [148]
[Zn2(ZnTCPP)(DNPI)1.5] (v/v= 3: 1)
23 PPF-21 DPT Zn-TCPP Zn2(COO)4 AB Bilayer CE heating/DEF-EtOH [148]
[Zn2(ZnTCPP)(DPT)] (v/v= 2: 1)
24 PPF-22 DPT Zn-TCPP Zn2(COO)4 ABBA Fsc CE heating/DMF-EtOH [148]
[Zn2(ZnTCPP)(DPT)1.5] (v/v= 2: 1)
25 PPF-25 BPY Zn-[trans-DCPP] Zn2(COO)4 - Ant CE heating/DMF-EtOH [154]
[Zn2(Zn(trans-DCPP)] (v/v= 3: 1)
26 PPF-27 BPY Zn-TCPP Zn2(COO)4 AB Bilayer CE heating /DEF-EtOH [149,151]
[Zn2(ZnTCPP)(bpy)]·2.5DEF·2H2O (v/v= 2: 1)
a
In this naming scheme, the first metal represents the porphyrin metal center, while the second metal represents the paddlewheel SBU metal node.

(ORR) and methanol oxidation [292]. In this work, the authors used
functional pyridine ligands on rGO basal planes as struts to link the
TCPP ligand, while preventing aggregation during formation of the hy-
brid rGO@Fe-Porph-MOF composite ((G-dye-FeP)n). Furthermore,
PCN-224/rGO nanocomposites were prepared by ultrasonic dispersion
of rGO in the DMF solvent containing TCPP and Zr(IV) precursors.
They were then subjected to a solvothermal reaction at 120 °C for 24h.
The SEM analysis confirmed the coexistence of rGO onto MOF frame-
work. However, the structural morphology of PCN-224 was significantly
influenced by the ratio of rGO (e.g., needle, granular, and amorphous
morphologies at rGO ratios of 0.08, 0.16, and 0.32, respectively) [293].
This may be attributed to the role of rGO as a nucleation template that
can direct/regulate the kinetic formation of PCN-224 framework. More
recently, Cu-TCPP⸦UiO-66/TiO2 (CTU/TiO2) composite photocatalyst
was prepared by in-situ coordination of Cu-TCPP ligand with UiO-66
during solvothermal growth from their precursors (i.e., Zr(IV) and
benzene-dicarboxylate ligand) in the presence of TiO2 dispersed parti-
cles and benzoic acid modulator. Results indicated that pure CTU (Cu-
TCPP⸦ UiO-66) exhibited octahedral microcrystals with sharp edges,
while slight self-agglomeration of TiO2 was observed on the external
crystal surface in the presence of 0.62% of TiO2 [294]. Therefore, it may
become difficult to control the formation of the desired core-shell struc-
ture using a direct synthetic strategy. Accordingly, LBL and two step
evaporation/transformation could be used as the most suitable proce-
dures to prepare guest@Porph-MOF composites as previously described
for the preparation of Co-TCPP-based MOF(Al) onto carbon cloth (See
Fig. 20 c) [254].
Post-synthetic approaches are used to increase the functionalization
variability of pre-assembled Porph-MOFs. In this regard, three post-
synthetic approaches have been investigated for custom design of
Table 7
List of some engineered Porph-MOF composites and their potential catalytic applications: a) photocatalysis, (b) electrocatalysis, and c) other oxidation/reduction reactions.

Sr. Functionalization Porph-MOF Guest molecules MOF framework Synthetic strategy (conditions) Application fields Ref.
No. strategy composites
Organic ligands SBUs Application Efficiency

[a] Photocatalytic applications

1 PSM with Ir(III) and HNTM-Ir/Pt Ir (1.05%) and Pt H4TCPP Zr(IV) Solvothermal growth in DMF (200μL Photoelectrochemical H2 201.9 mmol g-1 [261]
Pt(IV) metal salts at (2.54%) single-atoms H2O) at 120°C for 24 h production via water h-1 (stable over 3 runs)
80°C for 4h splitting
(autogenous
pressure)
2 PSM approach via [TP-222(Zn) 4-mercaptopyridine Zn(II)-TCPP Zr(IV) Solvothermal growth in DMF at 120°C Photocatalytic Photocatalytic kinetic rate (based on [359]
wet impregnation composite] anchored TiO2 for 72h. Then, 4-PySH@TiO2 or pure decontamination of dye) equal of 12.39 ×10-3 min-1 (4
process nanoparticles TiO2 NPs were encapsulated via organic pollutants reusable cycles), and effectively
(4-PySH@TiO2 NPs) solvothermal method at 120°C for 48 h. (e.g., RhB and MB dyes, accelerated in the presence of H2O2
and dinitrophenols) (Fenton-like catalyst)
3 PSM PCN-224 (Zr/Ti) Titanium as UMCs H6TCPP Zr(IV) Solvothermal method in DMF/acetic Photocatalysis Photodegradation of MB (N80%) and [318]

S.A. Younis et al. / Advances in Colloid and Interface Science 277 (2020) 102108
(post-metalation) acid at 65⸰C/72 h and the PCN-224 (Photo-redox reactions) antibiotic tetracycline (TC N 60%) as
product then post metallated with well as photo-reduction of Se(VI) in
TiCp2Cl2 in DMF at 120°C. visible region
4 PSM Al-PMOF(Zn)//Pt Post-metalation with H4TCPP Al(III) Hydrothermal reaction of H4TCPP Photocatalytic water H2 production [319]
(metalation; system Zn ions +AlCl3∙6H2O in water @180°C splitting at 100-200 μmol∙g-1 h-1 after 3h in
encapsulation) Pt nanoparticles followed by PSM by Zn metalation visible light
encapsulation followed by encapsulation with Pt
nanoparticle.
5 LBL thin film Pd@porphyrin FTO glass Free-metal or Pd(II) Zn2+ LBL deposition of SURMOF-2 Photovoltaic device Charge carrier mobility 0.003 -0.004 [320]
Zn-SURMOF-2@FTO metallated- counterparts from ethanol solution cm2 V-1 S-1
[15-diphenyl-10,20-di [spry time 25s and 15s for porphyrin
(4-carboxyphenyl) and Zn solutions] onto FTO surfaces
porphyrin
Pd(II))porphyrin]
6 In-situ growth NH2-rGO@ NH2-rGO H4TCPP Al(III) Solvothermal growth of PMOF in Photo-catalytic reduction Formate yield of 685.6 μmol g−1 h−1 [360]
process of PMOF in Al-PMOF. deionized water containing different of CO2 to formate in the (100% selectivity) at 5 wt% NH2-rGO
the presence of amounts of NH2-rGO at 180°C for 24 h. presence of TEOA
NH2-rGO guest

[b] Electrochemical/electrocatalysis applications

7 Post-synthetic Cyt c/CoTCPP-CPE cytochrome c (Cyto c) H4TCPP Co(II) Synthesis of Co-TCPP via solvothermal Electrochemistry Detection limit 1.1 μM [333]
encapsulation of MOF process at 160°C for 5d. Then, (sensor) and
onto carbon paste encapsulation of Co-TCPP MOF onto electrocatalytic oxidation
electrode (CPE) CPE via wet impregnation approach of NO2− during
followed by casting Cyt c on the surface biosensing
8 In-situ growth MOF-525/GNR-50 Graphene nanoribbons H4TCPP Zr(IV) Solvothermal growth MOF-525 in a Electrochemical catalytic Sensitivity 93.8 μAmM-1 cm-2 and a [361]
“self-assembly nanocomposite (GNRs) DMF suspension of GNRs at 80°C for oxidation and LOD of 0.75 μM
approach” 24 h sensor of nitrite
composite
9 Post-synthetic MOF-525/FTO thin Conducting glass of H4TCPP Zr(IV) Solvothermal growth of MOF-525 in a Electrochemical catalytic Sensitivity 95 μAmM-1 cm-2 and a [310,311]
layer-by-layer (LbL)- films fluorine-doped tin DMF suspension of GNRs at 80°C for oxidation and LOD of 2.1 μM
assembled oxide (FTO) 24 h sensor of nitrite
thin film
10 In-situ growth ZrPorph-MOF/MPC macroporous carbon Tetrakis(4-carboxyphenyl) Zr(IV) Solvothermal method through Electrochemical sensor Sensitivity 66 μAmM-1 cm-2 H2O2 [251]
“self-assembly composites (MPC) porphyrinato]-Fe (III) Cl growing Zr-PorMOF on MPC for (H2O2) and (0.5–137 μM; LOD 0.18 μM); while
approach” [FeTCPPCl] suspended in DMF developing for UA (5 -160 μM, LOD 0.14 μM), XA
for 48 h at 120°C multifunctional (5 -200 μM, LOD 0.052 μM) and HX
biosensors for uric acid (5-220 μM, LOD 0.49 μM)
(UA), xanthine (XA) and

(continued on next page)

39
 40
Table 7 (continued)

Sr. Functionalization Porph-MOF Guest molecules MOF framework Synthetic strategy (conditions) Application fields Ref.
No. strategy composites
Organic ligands SBUs Application Efficiency

hypoxanthine (HX)
11 In-situ growth (G-dye-FeP)n MOF rGO functionalized by H4TCPP Fe(III) Solvothermal in the presence of G-dye Electrocatalyst for ORR The electrochemical ORR current [292]
(pre-synthetic G-dye (5-50 wt%) in DMF/ethanol at 150⸰C/48h densities at −6.2 mA·cm−2, by
strategy) (G-dye 50 wt% -FeP)n MOF
12 In-situ growth (CoP)n/CNTs Oxidized MWCNTs 5,10,15,20- Co(II) In situ polymerization of multi-layer Electrocatalyst for water Faradaic efficiency of oxygen [362]
approach tetraethynyl-porphyrin framework oxidation production N86%
around the surface of oxidized MWCNT
using TMEDA
(tetramethylethylenediamine) and
CuCl as catalysts
In-situ growth Pt(II) Pt(II)TMPyP 4,5-imidazole-dicarboxylic In(III) Solvothermal synthesis of rho-ZMOF in Electrochemical sensing Detection limit 27 nmol [363]
approach TMPyP@rho-ZMOF (TMPyp=tetrakis acid (4,5-H3ImDc) the presence of Pt(II)TMPyP guest in for iodide and sulfide
(N-methyl-4 pyridyl) reaction media (ethanol/DMF) at anions in organic phase

S.A. Younis et al. / Advances in Colloid and Interface Science 277 (2020) 102108
porphyrin) 105⸰C/48-72h (methanol)
13 Drop-casting thin ZnPorph@SURMOF Three MPs molecules: 1,4-benzenedicarboxylic Zn(II) Direct drop casting of MPs from Light-emitting Time-resolved emission lifetime [364]
film PdPorph@SURMOF (1) Octaethyl- or ethanol solution inside SURMOF from 3.6±0.2 μs to 2.06±0.05 ns
(Porph@MOFs) PtPorph@SURMOF 21H,23H-porphine Zn Cu(II)
(SURMOFs= (II) or Pd(II); (2)
Surface-anchored 5,15-diphenyl-10,20-di
MOFs) (4-carboxyphenyl)
porphine Pd(II); (3)
TCPP based Zn(II) and
Pt(II)

[c] Other catalytic application [e.g., CO2 reduction and catalytic oxidation reactions]
14 De Novo synthesis of MTV-MOFs -- H4TCPP Zr(IV) Solvothermal growth in acidified DMF Catalytic conversion of 64±5% conversion (90% selectivity) [332]
mixed ligand MOF (TCPP⊂Im-UiO-66) + (acetic acid) at 120°C for 12 h CO2 into cyclic carbonate
15 followed by MTV-MOFs Br- ions 2-(imidazol-1-yl) PSM of TCPP⊂Im-UiO-66 using using allyl glycidyl ether
78±2% conversion with low
sequential (TCPP⊂(Br−) terephthalic acid bromoethane at 80°C for 48 h (N2 at 1 bar. selectivity (65%) due to large Br-
post-synthetic Etim-UiO-66) atmosphere) amount within framework
-
16 strategies for MTV-MOFs Zn(II) + Br ions PSM of (TCPP⊂(Br−)Etim-UiO-66 77±2% conversion (92% selectivity
ionization and ZnTCPP⊂(Br−) with ZnBr in DMF at 100°C for 24h and 98% yield) and 19.8 – 91.1% yield
metalation Etim-UiO-66) for catalytic conversion of epoxides
approaches and CO2 reactions. Enhanced
catalytic activities (3 cycles) due to
the cooperative effect of Zn(II) UMC
and Br- ions
17 Layer-by-layer (LbL)- Mg-L2-MOF TCPP & MgTCPP BPY Zn(II) Solvent-assisted linker exchange Ligand exchange from BPY to MgTCPPM and formation of new [289]
assembled thin-film (SALE) or PSE and post-assembly MgTCPP-MOF thin-film
linker metalation
18 In-situ growth CuTNPP@MOF Meso- tetrakis 1,1-bis-[3,5-bis(carboxy) Cu(II) Solvothermal condition in DMF at 85°C Catalytic oxidation of 60% catalytic conversion of DBTC in [365]
“self-assembly MnTNPP@MOF [4-(nicotinoyloxy) phenoxy]methane (H4L) for 120 h 3,5-di-tert-butylcatechol 2h by CuTNPP@MOF and catalytic
approach” phenyl]porphyrin (DTBC) in the presence stability up to 4 cycles
(TNPP) or MnTNPP of H2O2 at ambient
conditions
19 Self-assembly and [Mn+-RTMPyP] cationic [H2TMPyP]4+ 4,5-imid-azoledicarboxylic In(III) Solvothermal reactions of In(NO3) Catalysis Hydrocarbon oxidation [326]
Post-metalation (Mn+= Mn, Co, Cu porphyrin {[H2TMPyP] acid 3·xH2O and 4,5-imidazoledicarboxylic [yield= 91.5% and (TON of 23.5
or Zn) [p-tosyl]4} acid (H3ImDC) in an DMF/CH3CN (catalyst loading of 3.8%)]
mixture to yield rho-ZMOF in the pres- using Mn-RTMPyP
ence of ([H2TMPyP] [p-tosyl]4) por-
phyrin then post-metalation with Mn,
Cu, Zn or Co ions
20 PSM Fe@Hf-2 FeCl3 Meso-tetra Hf6-oxo Solvothermal reaction in DMF Catalysis 100% tandem styrene [330]
(post-metalation) (Hf-NU-1000) (4-carboxyphenyl) clusters epoxidation–epoxide
porphyrin-Fe(III) chloride ring-13opening reaction in 10h
 S.A. Younis et al. / Advances in Colloid and Interface Science 277 (2020) 102108
guest@Porph-MOF composites such as post-synthetic modification
(PSM), post-synthetic exchange (PSE), and post-synthetic deprotection
(PSD) [14,24,97,275,289,295,296]. Among these procedures, PSM is the
most commonly used strategy. It can be carried out through solid-state
mixing or wet-impregnation of guest molecules onto the outer surface
of pre-synthesized frameworks [14]. For example, the PCN-224/
MWCNT composite was prepared as an electrocatalyst for oxygen re-
duction by dispersing different weight ratios of the pre-assembled
PCN-224 to functionalize MWCNT in ethanol followed by exposure to
ULS radiation [253]. More recently, an ultrathin 2D Cu-TCPP(Fe) MOF
was solvothermally prepared under controlled reaction of Cu(II) salt
with TCPP(Fe) using trifluoroacetic acid and PVP additive. Subse-
quently, the 2D Porph-MOF/GOx hybrid nanocatalyst was prepared by
the physisorption of glucose oxidase (GOx) onto Porph-MOF via a
post-synthesis approach. The catalytic results confirmed the enhanced
performance of a 2D Porph-MOF/GOx hybrid, similar to peroxidase-
like activities for in vitro and in vivo wound healing [297]. However,
three different types of hybrid products might be formed when using
these post-synthetic methods: i) separate free mixtures of two solids
(i.e., undesired), ii) partially formed guest@host composites with free
unreacted guest molecules, and iii) a desired composite of a guest@
host hybrid structure [13]. Hence, post-synthetic acquisition of the de-
sired hybrid composite via PSM is limited because it is challenging to
spatially regulate the interaction and distribution between guest mate-
rials and Porph-MOF frameworks.
To address these problems in custom-design functionalities, another
PSM method can also be carried out via chemical functionalization of or-
ganic ligand/metal sites of a pre-assembled framework (e.g., post-
metalation and functionalization of porphyrin ligand) without influenc-
ing the crystal lattice structure [173]. More specifically, the porphyrin li-
gand can be modified via (a) covalent modification (or elaboration) and
(b) electron addition (reduction) and concomitant incorporation of
charge compensating ions [298]. Furthermore, modification of metal-
containing nodes can be achieved via (a) incorporation of pendant li-
gands or a non-framework via dative (axial) bonding to coordinatively
UMCs sites (See PPF series in Fig. 22 and Table 6), (b) grafting of alkyl,
amine, or silyl protecting groups to oxygen atoms in POM and metal-
oxide clusters, and (c) attachment of UMC metal ions or POM complexes
(See Section 5.4) at node oxygen sites through atomic layer deposition
or reaction with organometallic species in dry solutions [298]. More-
over, PSE, also known as building block replacement, has been explored
as a means of immobilizing the MP active species in the pre-assembled
robust framework to alter its features [289][299]. For instance, porous
MOM-10 [{Cd6(bpt)4Cl4(H2O)4}; bpt = biphenyl-3,4',5-tricarboxylate]
is an ionic framework structure produced via solvothermal coordination
of bpt ligand with [Cd3Cl2(COO)6] SBU [300]. Another porph@MOM-10
(MOM= metal− organic materials) hybrid was also produced via the
PSM method by encapsulation of CdTMPyP (TMPyP = meso-tetra(N-
methyl-4-pyridyl)porphyrin tetratosylate) counterion clusters in the
MOM-10 ionic framework. After that, both the Cd(II) ions in the
MOM-10 (as SBU) and CdTMPyP (as UMC) were partially or completely
exchanged by either Cu(II) or Mn(II) metal sites, respectively, (via the
PSE method) to catalyze an epoxidation reaction process. For this case,
the SALE and non-bridging ligand replacement are the two most exten-
sively applied approaches to design the functionality of Porph@MOF hy-
brid composites [13]. In fact, such a PSE method also induces an
alteration in the SBU topology via the formation of tetranuclear [Cu4X2
(COO)6] clusters with relatively large Cu-SBU (e.g., by 20% relative to di-
nuclear [Cd2(COO)6] in the parent framework) [300,301]. Trans-
metalation at the inorganic cluster and porphyrin core represent one
of the most widely used procedures during PSE-type functionalization.
For instance, the functionalized Mn+Porph@MOF composite success-
fully inhibits self-dimerization of active UMC sites via axial coordination
with other ligands while retaining the permanent porosity feature of
the parent framework. Hence, the functionalized hetero-metal catalytic
sites can easily be isolated and protected by encapsulation of free-base
41
or metallated porphyrin functionality within regular MOFs [97,275].
For example, post-synthetic metalation of metal nodes and porphyrin
core was reported for a family of porphyrin-salen-based chiral MOFs
{[Cd2(NiL1)(CdL2)][Cd2(NiL1)(H2L2)]·6DMF·5MeOH} in which the Cd
formed twisted Cd2(COO)4 paddlewheel SBUs and Cd-based UMCs oc-
cupied porphyrin rings [302,303]. In this case, the framework was pre-
pared by solvothermal coordination through the reaction of tetra-(4-
carboxyphenyl)porphyrin (H6L2), (R,R)-N,-bis(3-tert-butyl-5-(4-pyri-
dyl)salicylidene)-1,2-diphenyldiamine Ni(II) (NiL1) and Cd nitrate
salts. Such a parent framework was post metallated by soaking in
DMF solution with Cu(II), Ni(II), Zn(II), and Co(II) to produce four
types of bimetallic paddlewheel SBUs (e.g., Cd–Cu, Cd–Zn, Cd–Ni, and
Cd–Co). However, the results also reflected the partial post-exchange
of Cd sites in both SBU and UMC sites [303].
Furthermore, PSD is another intuitive post-synthetic strategy for
deprotection of linker functionality and incorporation of multiple func-
tionalized groups to produce complex multifunctional MFSs-MOFs
products [304]. Similar to a regular framework, the synthetic processes
can be carried out by three distinct steps in a single reaction pot: (1)
grafting a protected group (i.e., amine or silyl group) onto the metal cen-
ters, (2) in-situ functionalization of an organic porphyrin ligand (i.e.,
Brønsted acid/base as an organic spacer), and (3) subsequent
deprotection of the grafting moiety on the metal centers [13,15,305].
In this case, the use of a protected functional moiety during one-pot
solvo(hydro)thermal assembly of the MFSs-MOF crystals was indis-
pensable to prevent framework interpenetration [89,304]. In a topolog-
ical sense, neither network can be separated from the entanglement
without deformation of the engineered crystals (i.e., breaking bonds)
[306,307]. For example, when using amorphous silica as a template
agent to achieve a high degree of porosity in a PAF-1 structure, the tet-
rahedral node-to-node distance in the PAF-1 framework was not suffi-
cient for preventing interpenetration or formation of a mesoporous
network (i.e., there are no permanent pores) [304]. Therefore,
porphyrin-centered elongated tetratopic linkers, rather than inorganic
templates, have been used extensively in the assembly of non-
interpenetrated functionalized Porph-MOF topologies (e.g., See
MMPF-8, Fig. 16).
6.2. Applications of functionalized Porph-MOF-based composites
Controllable design and functionalization of Porph-MOF-based com-
posites (e.g., Porph@MOFs or guest@Porph-MOFs) ensures further im-
provement in material stability while opening up new opportunities
for diverse applications as summarized in Table 7.
6.2.1. Electrocatalysis and electrochemical sensors
To overcome challenges arising from the use of noble metal nano-
particles for electrochemical and electrocatalysis applications, various
Porph-MOFs have been introduced and utilized to improve electro-
chemical/catalysis selectivity for certain products [194,308,309].
Porph-MOFs are promising non-noble metal electrocatalysts and pos-
sess superior electrochemical/catalytic activities (for ORR, the hydrogen
evolution reaction (HER) and oxygen evolution reaction (OER)) because
of their designable structures with large surface area, tunable porosity,
and homogeneous dispersion of different open coordinative metal cen-
ters (such as active OM-based SBU and UMC-based porphyrin core).
Here, we particularly focus on Porph-MOFs that incorporate
electrocatalytically-active guest sites into the framework either via
pre- or post-synthetic methods.
Recently, uniform solvothermal LBL growth of free-base TCPP-MOF
(Zr)-525 thin films on a conducting FTO glass (0.25 cm2) substrate
was reported using free-base H4TCPP linkers and hexa-zirconium
nodes [310,311]. The constructed TCPP-MOF(Zr)-525 (BET 2415 cm2/
g) thin film was stable and electrochemically active and was used for ef-
ficient electrocatalytic oxidation and amperometric measurement of ni-
trite (20 to 800 μM) in 0.1 M KCl aqueous solutions (Fig. 23a). The
42 S.A. Younis et al. / Advances in Colloid and Interface Science 277 (2020) 102108
amperometric nitrite sensor built on a TCPP-MOF(Zr)-525@ FTO thin
film was sensitive (95 μA/mM-cm2) by virtue of faster charge-
transport rates and offered a low LOD of 2.1 μM. (Co)TCPP-MOF525@
FTO thin films were prepared through direct growth of Co-TCPP onto
FTO substrates by replacement of Zr4+ with Co2+ in metal sites in the
above thin-film system [312]. This new (Co)TCPP-MOF525@FTO thin
film had electro-catalytic activities toward CCl4 reduction. The (Co)
TCPP-MOF525 crystal did not directly show reduced activity for CCl4
due to its insulating nature; however, deposition of the material onto
the FTO conducting surface facilitated charge conduction via charge
transfer through a hopping mechanism (Fig. 23b). Accordingly, cyclic
voltammetry showed that the above thin-film supported an improved
current density. Further, spectro-electrochemical studies proved that
the catalysis properties of the (Co)TCPP-MOF525@FTO thin film were
sustained even during long-term use. Nonetheless, some degree of dete-
rioration was observed due to the release of (Co)TCPP over time [313].
An rGO-porphyrin MOF [(Fe-P)n MOF: rGO@(Fe-TCPP)MOF)] com-
posite was produced by functionalizing the rGO surface and then
using it as an interlayer during the growth of (Fe)TCPP-MOFs [292].
The above composite consisted of different weight percentages of func-
tionalized rGO sheets with a pyridine-terminated dye (G-dye; 5-50 wt
%) and iron-TCPP linker. This composite offered better electrocatalytic
activity and selectivity toward the ORR reactions in an alkaline medium,
with an onset potential of ~ 0.93 V vs. RHE due to the unique intercon-
nection between the G-dye functionalized graphene-porphyrin within
the composite. In contrast, the increased incorporation of G-dye influ-
enced the (Fe-P)n MOF crystallinity. The effect of G-dye on the frame-
work crystallinity was confirmed by marked lattice distortion and
morphology change of the (Fe-P)n MOF from a plate to a rod shape
with an increase in G-dye content to 10 wt%. Moreover, the higher po-
rosity along with large bond polarity in the composite afforded a near
4-electron ORR pathway [314]. The produced composite possessed a
significantly reduced methanol crossover effect compared with a com-
mercial Pt catalyst. This was ascribed to the unique synergistic interac-
tions between the rGO and Porph-MOF that improved the charge
transport within the porous scaffold structure. Consequently, rGO@
(Fe-TCPP) MOF was recommended by the authors as a promising Pt-
free cathode in alkaline direct methanol fuel cells (DMFCs).
Taking inspiration from the previously mentioned (Co)TCPP-MOF,
the Co-TCPP porphyrin was interconnected through Al2O3 rods to pro-
duce a new 3D (Co)TCPP-MOF(Al) framework [315]. The generated
3D (Co)TCPP-MOF(Al) was directly deposited onto ITO without binders.
This PSD method utilized the atomic layer deposition of an aluminum
oxide layer onto the ITO, followed by the direct growth of a Porph-
MOF (Al) film [316]. The (Co)TCPP-MOF(Al)@ITO film enhanced the
electroactivity of the MOF (Co-based UMCs of 1.1 × 10−7 mol cm−2),
which led to improved electro-catalytic performance toward generation
Fig. 23. Crystal structures and catalytic properties of pure MOF-525 and Co)TCPP-MOF@ FTO composite: (a) Crystal structure of MOF-525 along with amperometric plot of current density
vs. concentration of nitrite and cyclic voltammetry curve of Jpa/ν0.5 vs. ν obtained from the amperometric curves of the MOF-525@FTO thin film measured at 0.9 V in a solution containing
1.0mM nitrite. Reproduced from [310]. (b) A schematic attachment of the (Co)TCPP-MOF@ FTO and its proposed charge hopping mechanism. Reproduced from [312,313].
of the CO•−2 radical in the presence of CO2 with an increase in current
density from 3.5 to 5.9 mA cm−2 at E1/2 = −0.5V vs. RHE. Thus, during
controlled potential electrolysis (CPE), the (Co)TCPP-MOF(Al)@ITO film
exhibited high selectivity for CO2 reduction to CO (TONs of 1400 per cat-
alytic site) and CO production in an aqueous solution (76% Faradaic ef-
ficiency at Epc = −0.7V vs. RHE). In another example, a system of
(Fe)-TCPP-MOF-525 was electrophoretically deposited onto the FTO
conductive substrate and was used for electrocatalytic reduction of
CO2-TCPP [317]. The initial electrochemically accessible active area of
Fe-TCPP was calculated to be 0.62 × 10−7 mol cm−2 (77% of the MOF
surface area), which was lower than that of Co-TCPP. The CPE at Epc =
−1.3 V vs. NHE resulted in higher CO2 reduction with a Faradaic effi-
ciency of up to 100% over 5 h (CO = 54-60%, H2 = 45-41%, with TON
= 272 in the absence and presence of 2,2,2-trifluoroethanol). The
higher Faradaic efficiency is fundamentally related to the Fe (1/0)
redox couple at E1/2 = −1.4 V vs. NHE. This suggestion was based on ev-
idence for mechanistic cleavage of a CO2 bond in the homogeneous sys-
tems; namely, a Fe–CO2 adduct formed, followed by the release of CO
[313].
6.2.2. Photo-catalysis and photon-response activities
Functional Porph-MOFs have attracted much attention as a light-
harvesting antenna because of their efficient engagement in energy/
electron transfer processes. Studies have shown that the
photogenerated photons can transfer over 10–30 porphyrin building
blocks within their lifetime, with a high anisotropy along a preferred di-
rection [314]. However, due to their limited photon absorption bands in
the visible spectrum of solar energy, different synthetic strategies are
employed (including self-assembly and PSM) for improving the
photo-response of Porph-MOFs in visible light [164]. For example,
Wiederrecht, Hupp, and co-workers (2013) presented the formation
of a guest-host Porph-MOF composite (with quantum dots “QDs”) to
enhance light harvesting via energy transfer from the QDs to the
MOFs (Fig. 24). The Porph-MOF composites consisted of CdSe/ZnS
core-shell QDs coated with a monolayer of polyethylene glycol (PEG)
and an NH2-functional amphiphilic polymer. QDs were then
immobilized on the exterior surface of (Zn)TCPP-MOFs through
amine–Zn coordination [164]. The simulated photo-generated excitons
in the QDs were transferable to the Porph-MOFs within the visible solar
spectrum through resonance energy transfer.
Time-resolved fluorescence analysis in Fig. (24) indicates a reduc-
tion in the lifetimes of QDs, and quantum efficiency of up to 84% could
be achieved. In addition, the number of photons harvested by (Zn)
TCPP-MOFs increased by N50%. Inspired by the fact that most MP ligands
are also natural photo-sensitizers (such as chlorophyll a), the post-
metalation (porphyrinic core) of primitive Porph-MOFs has recently
drawn significant attention. They can act as efficient photo-catalysts
 S.A. Younis et al. / Advances in Colloid and Interface Science 277 (2020) 102108
Fig. 24. Schematic of QDs@(Zn)Porph-MOFs (QDs= CdSe/ZnS) and its features for enhanced photocatalytic performance: a) Diagram of QDs@(Zn)Porph-MOFs to improve light harvesting
via QDs- Zn(Porph) energy transfer. b) Optical microscopy image of a plate-shaped (Zn)Porph-MOF framework. c & d) Fluorescence decays of CdSe/ZnS QDs (core–shell) of different sizes
(QD550 and QD620) on glass and two (Zn)Porph-MOFs. Reproduced from [164,314].
due to reduced diffusion restrictions and extension of the response to
the visible region [261,318]. However, with regard to their application
as photocatalysts, Porph-MOFs show relatively low chemical stability
in aqueous solutions due to the low-oxidation of metal nodes (soft
acids). This limitation has been addressed by using mixed hetero-
metal nodes with enhanced stability. In this case, Porph-MOFs in the
PCN series (like PCN-224) constructed with Zr–oxo metal clusters coor-
dinated to a metal-free TCPP carboxyl linker have attracted intensive in-
terest. These MOFs are formed with a post-metalation approach using
titanium ions as photo-catalytic active UMC sites. The inoculation of
Ti-UMC active sites within PCN-224 (Zr) via a PSM strategy (cation ex-
change method) can drive efficient enhancement in photocatalytic ac-
tivities of the resulting PCN-224 (Zr/Ti) MOFs with mixed Zr- and Ti-
oxo clusters (Fig. 25a) in a relatively facile and low-cost manner
[261,318]. It was demonstrated that Zr could be substituted by 38.6%
Ti after 8 days of the cation exchange reaction, and the obtained product
showed no significant difference in morphology. Notably, PCN-224(Zr/
Ti) showed a great improvement in visible light-driven photocatalytic
oxidation (e.g., of methylene blue; N 80%) and reduction (e.g., of Se
(VI) using photo-chemical vapor generation with formic acid as the
sacrificing agent) (Fig. 25).
Similar to pure PCN-224, the detected photo-redox activity of PCN-
224(Zr/Ti) was found to maintain its stability up to 3 cycles. Also, the
PCN-224(Zr/Ti) had higher activity than that of ZrO2 and TiO2 catalysts.
The above enhancement in the kinetics of the photocatalytic redox pro-
cesses was attributed to improved photon adsorption, favorable
electron–hole separation, and fast electron transfer from TCPP to both
Zn and Ti-oxo-clusters. Compared to PCN-224 (Fig. 25b), incorporation
of Ti3+ into PCN-224(Zn) caused a distinct decrease in the calculated
lifetime and photoluminescence (PL) decay curves (0.18 ns), which
were fitted by a bi-exponential function. Moreover, PCN-224(Zr/Ti)
displayed a smaller arc radius in the EIS (electrochemical impedance
spectroscopy) Nyquist plot (band gap 1.76 eV) than that of PCN-224
(band gap 1.86eV) (Fig. 25c). The smaller arc radius in the EIS of PCN-
224(Zr/Ti) MOF confirmed its lower resistance for interfacial charge-
43
transfer (i.e., accelerated charge-transfer) relative to the pristine PCN-
224 framework. Two other water-stable microporous Al-PMOFs (quan-
tum yield 0.01% in 15 h) based on coordination of an Al metal center
with either TCPP-porphyrin or Zn-TCPP (produced by PSM) were con-
structed and suggested for use in photocatalytic water splitting and hy-
drogen production under visible light [319]. After post-synthetic
metalation of TCPP with Zn to produce Al-PMOF(Zn), the Soret band in-
creased from 415 to 425 nm with the appearance of two Q bands in the
UV-Vis spectrum instead of four, resulting from the higher symmetry of
the metallated Al-PMOF(Zn) compound. In contrast, the photocatalytic
activity of the system was improved by more than one order of magni-
tude after post-synthetic immobilization of Pt on the Al-PMOF (Zn),
with a hydrogen generation rate of 100-200 μmol g-1 h-1 in visible
light after 3 h.
Moreover, one of the appealing features of Porphyrin@MOF struc-
tures is their ability to preserve the attractive native characteristics of
the porphyrin. In this respect, the MOF host offers the outstanding ben-
efit that molecular porphyrin thin films with a porphyrin-organic guest
can be prepared on organic photovoltaic cells with a particular structure
in a straightforward fashion [9]. In fact, many molecular porphyrins thin
films are currently employed successfully to convert absorbed solar-
light into electricity through photovoltaic cells. Comparatively, the ap-
plication of Porph-MOF crystals in photovoltaic cells is still challenging
because of crystal defects that form during uncontrolled synthesis;
these hamper their efficient utilization in this field. For example, a series
of porphyrin@SURMOFs hybrid structures were synthesized by the
liquid-epitaxy (LPE) approach, as has been reported in dye-sensitized
solar cells (DSSC) and solid-state photovoltaic devices (Fig. 26) [320–
322]. One such porphyrin@SURMOF provided an incident photon flux
efficiency of ϕ=3.0×10-1 cm-2 s -1; however, the total efficiency of
power-to-electricity yield was rather low in a practical case (b1%) [9].
This low performance possibly resulted from slow charge mobility and
electron-hole recombination in a metal-free base porphyrin
[166,323,324]. Thereby, further post-metalation or use of MPs and/or
attachment of electron-donating groups to the porphyrin ring can
44 S.A. Younis et al. / Advances in Colloid and Interface Science 277 (2020) 102108
substantially increase the charge carrier mobility, which consequently is
expected to improve efficiency for photo-induced charge carrier
generation [9].
6.2.3. Other types of catalytic applications
For water splitting, Morris and co-workers (2016) immobilized Ni-
TCPP as an active water oxidation promoter into PCN-224 containing
highly oxophilic metal ions (i.e., Zr(IV)) via a solvothermal PSE reaction.
Accordingly, the produced (Ni)TCPP-PCN-224 (Zr) MOF thin film was
found to electrochemically facilitate water oxidation near-neutral pH
(Fig. 27a) [325]. Next, a (Ni)TCPP-PCN-224 (Zr) MOF thin film was di-
rectly grown on FTO via a solvothermal reaction of ZrCl4 and Ni(TCPP)
in the presence of formic acid as a modulator. The CV curves showed
an increase in current density for a PCN-224 MOF film containing
NiTCPP (Faradaic efficiency up to 35%, at Epa = +1.0 V vs. NHE),
which was comparable to that of the FTO substrate as well as PCN-224
alone (Fig. 27b). This implies that oxidation of the Ni(TCPP) ligand
was effective for water splitting. Also, the current-voltage (Tafel) plot
had a slope of 150 mV dec−1, indicating that an electrochemical oxida-
tion mechanism can induce the chemical transformation of oxygen (Fig.
27c) with a steady-state current density. Tafel analysis proved the good
electrochemical oxidation power of NiTCPP, which functioned as a ho-
mogenous catalyst for improved water splitting (Fig. 27d). The mecha-
nistic steps of the OER using Tafel analysis were consistent with
electrochemical oxidation of the porphyrin macrocycle and Ni(TCPP)
metal centers [313].
Furthermore, post-synthetic encapsulation of MPs as active guest
molecules in the porous cavities of MOF frameworks has been proposed
for biomimetic catalytic applications [326–328]. This post-synthetic ap-
proach is unique in that it simulates natural catalytic enzymes (such as
heme enzyme by encapsulation of iron-porphyrin active centers) [329].
In this manner, iron tetrasulfophthalocyanine (FePcS) as a
metalloporphyrin isomer has been irreversibly immobilized into
nanocages of the MIL-101 to produce a hybrid FePcS@MIL-101 compos-
ite (MIL= Matérial Institut Lavoisier) [329]. The obtained composite
showed a superior selective catalytic activity for liquid-phase oxidation
of aromatic substrates with tBuOOH (95% conversion) compared to the
homogeneous FePcS catalyst itself. Consequently, encapsulation of cata-
lytically active MPs in the porous MOF crystals can synthesize materials
with critical catalytic properties mimicking those of benign enzymes.
For example, Eddaoudi and co-workers reported in-situ encapsulation
of cationic [H2TMPyP]4+ porphyrin in an anionic zeolite-like MOF con-
taining In3+ ions metal sites coordinated with a 4,5-imid-
Fig. 25. The photo-redox catalytic mechanism of PCN-224 (Zr/Ti) along with a) crystal structure and PSM strategy for incorporation of Ti into PCN-224(Zr) frameworks via cation exchange
process, b) time-resolved PL spectra, and c) Nyquist plots of PCN-224 comparable to PCN- 224(Zr/Ti) and a mixture of PCN-224 and TiCp2Cl2 under visible light. Reproduced from [261].
azoledicarboxylic acid (H3ImDC) linker via self-assembly [326]. Post-
metalation was conducted with different transition metal ions (such
as Mn, Cu, Zn or Co) in the encapsulated [H2TMPyP]4+. The resulting
MP@rho-ZMOF composites can serve as catalysts for hydrocarbon oxi-
dation. Following a similar approach, Fe3+-and Mn3+-based tetrakis
(4-sulphonatophenyl)porphyrin can be encapsulated in the nanocages
of HKUST-1. Using this approach, the resulting composite was able to
mimic the capability of heme enzymes in terms of both catalytic reactiv-
ity and structure [327].
Furthermore, another biofunctional mesoporous Hf-NU-1000 MOF
(denoted Fe@Hf-2) prepared from the post-metalation of Hf-2 frame-
work using anhydrous FeCl3 in a DMF solution was found to catalyze
the tandem styrene epoxidation–epoxide ring-opening reaction with
complete conversion within 10 h [330]. Surprisingly, these authors pro-
posed that the bis-μ-oxo di-iron functionality on the produced Fe@Hf-2
Hf6 nodes contributed to the inverse selectivity [16]. The Hf-2 frame-
work has a topology analogous to PCN-222 (MOF-545) with Hf6-oxo
SBU clusters and a meso-tetra(4-carboxyphenyl)porphyrin-Fe(III) chlo-
ride linker.
7. Summary and remarks
This review highlighted the crystal engineering concepts of
porphyrinic porous coordination polymers (Porph-PCPs, including
Porph-MOFs/COFs) and illustrated the historical development and clas-
sification of the classical frameworks. A survey of the literature con-
firmed that the solvothermal approach is the principal route for
construction of Porph-PCPs. In addition, most of the developed Porph-
PCPs act as catalysts. Principally, the catalytic performances of Porph-
PCPs depend on the type and coordination mode of the unsaturated
metal centers (UMCs) and secondary building nodes. Thus, synthetic as-
pects of various functional Porph-MOFs are addressed based on the
types of inorganic nodes (i.e., metal ions or supramolecular building
units “SBUs”) and polytopic porphyrin ligands (i.e., structure and
functionality).
Apart from the use of porphyrinic ligands, particular focus has also
been given to the synthesis strategies of different types of SBU nets
(mono-, bi-, tri- and fourth-nuclear SBUs) to control the formation of
Porph-MOF networks. Controllable formulation of porous Porph-MOFs
is often unpredictable due to the following reasons: 1) large varieties
of supramolecular isomerism in synthetic porphyrin molecules and 2)
an uncontrolled coordination environment for the metal centers in
metal-free-based porphyrin cores and exocyclic functional moieties.
 S.A. Younis et al. / Advances in Colloid and Interface Science 277 (2020) 102108 45

Fig. 26. LBL synthesis scheme for Porph@MOF thin film for photovoltaic application: (a) Schematic of the LPE approach for thin film fabrication of Porphyrin@ SURMOF with a series of
porphyrin linkers in LBL fashion. Reproduced from [9,368]. (b–d) Architectures of Porphyrin@ SURMOF thin film-based photovoltaic devices and (c)–(e) their corresponding J–V
curves. (b) and (c) reproduced from [320]. (d) and (e) reproduced from [321].

To improve the controlled synthesis, we thus summarized the coordina-
tion of porphyrin isomers with both hard and soft Lewis metal sites
using high throughput (HT) techniques to design well-defined Porph-
MOFs. As such, recent advances in HT strategies were highlighted in-
cluding microwave, mechanical/sonochemical, electrochemical,
contra-diffusion, and ionic liquid (ILs)/SC CO2 fluids. However, HT-
synthesis approaches have not been fully explored, and only a few re-
ports are available that describe the controlled synthesis of porphyrinic
MOF structures. Such “out-of-the-box” HT methodologies remain one of
the soundest future research avenues for demonstrating how the struc-
ture and topology of Porph-PCPs macromolecules might progress fur-
ther with tunable and predicted properties for various sophisticated
disciplines.
To gain a better understanding of the synthesis strategies, the critical
factors affecting topology, geometry, and dimensionality of Porph-MOF
structures have been discussed. The mechanism of Porph-PCP crystal
growth and associated structure properties are affected by many vari-
ables including the nature of the solvent, metal/linker concentration
(and ratio), reaction period, reaction additive, and synthesis tempera-
ture. Therefore, the nucleation and growth of crystalline frameworks
were briefly addressed to highlight synthetic protocols for commercial
production of Porph-MOFs families such as (1) the pioneering Porphy-
rin Illinois Zeolite Analogue (PIZA), (2) metal/metalloporphyrin frame-
works (MMPFs), (3) Porphyrin Pillared Frameworks (PPF), and (4)
Robust Porphyrin Materials (RPM). In addition, the disposition or ex-
change functionality (via incorporation of either possible chemical moi-
eties or guest molecules) plays a key role in expanding the potential
applicability of Porph-MOFs. In this case, it was found that altering the
linked MP central atoms via coordination chemistry can change
Porph-MOF functionality without changing topology structure. Like-
wise, engineering of Porph-MOF composites via combination or scaf-
folding with functional elements to form guest@host composite
structures can also be used as an alternative strategy to enhance their
overall physicochemical properties. In addition, (Porph)MOF-based
hosts can encapsulate numerous nano/macro-based guest molecules
(e.g., functional moieties, nanomaterials, polymers, carbon conducting
46 S.A. Younis et al. / Advances in Colloid and Interface Science 277 (2020) 102108
Fig. 27. Schematic topology of (Ni)TCPP-PCN-224 (Zr) MOF thin film and its electrochemical activities: a) PCN-224 structure with the Ni(II)to-Ni(II) distance illustrated [color index:
carbon: grey; oxygen, red; nitrogen, blue; nickel, green; zirconium, light blue]. b) CV of (Ni)TCPP-PCN-224 in 0.1 M TBAPF6/CH3CN (black) with increasing H2O concentrations. c) SEM
& XRD results of solvothermally prepared (Ni)TCPP-PCN-224 on FTO. d) Proposed mechanism for the electrochemical water oxidation reaction catalyzed by (Ni)TCPP-PCN-224.
Adapted with permission from [325].
substrates, and biological substrates like enzymes, genes, proteins, and
DNA) through topological entrapment via pre- and post-synthetic
processes.
Remarkably, post-synthetic strategies can provide the possibility of
incorporating/encapsulating large numbers of varied functionalities of
specific interest into Porph-MOFs while preserving the framework in-
tegrity, which is not necessarily achievable via de novo direct assembled
approaches. Therefore, in this review, the reported features related to
Porph-MOF composites, and their classifications have been summarized
according to the synthesis strategies and the nature of the guest mole-
cules (i.e., guest@Porph-MOFs and Porph@MOFs systems) for target ap-
plications. We believe that the combination of the molecular-scale
synthesis tunability of Porph-MOF platforms and the ability to control
their sizes can help create useful materials for many scientific applica-
tions. The Porph-MOF materials can offer enhanced multifunctional ac-
tive sites, superior mechanical stability (even under harsh conditions),
conductivity, storage, (bio)sensing, (bio)imaging, good optical proper-
ties, and better catalytic effectiveness. Thus, it is clear that a better
knowledge on Porph-MOF/COF systems can result in their use as new
functional materials in many scientific fields.
Acknowledgements
We would like to acknowledge support from the R&D Center for
Green Patrol Technologies through the R&D for Global Top Environmen-
tal Technologies funded by the Ministry of Environment (MOE), as well
as by a grant from the National Research Foundation of Korea (NRF)
funded by the Ministry of Science, ICT, & Future Planning (Grant No:
2016R1E1A1A01940995).
References
[1] Rogge SMJ, Bavykina A, Hajek J, Garcia H, Olivos-Suarez AI, Sepúlveda-Escribano A,
et al. Metal-organic and covalent organic frameworks as single-site catalysts. Chem
Soc Rev 2017;46:3134–84. https://doi.org/10.1039/c7cs00033b.
[2] Morsali A, Hashemi L. Main Group Metal Coordination Polymers: structures and
nanostructures. Hoboken, New Jersey: Scrivener Publishing LLC, John Wiley &
Sons, Inc.; 2017. https://doi.org/10.1002/9781119370772.
[3] Zhu R, Ding J, Jin L, Pang H. Interpenetrated structures appeared in supramolecular
cages, MOFs, COFs. Coord Chem Rev 2019;389:119–40. https://doi.org/10.1016/j.
ccr.2019.03.002.
[4] Hu H, Yan Q, Ge R, Gao Y. Covalent organic frameworks as heterogeneous catalysts.
Cuihua Xuebao/Chinese. J Catal 2018;39:1167–79. https://doi.org/10.1016/S1872-
2067(18)635057-8.
[5] Sun J-K, Yang X-D, Yang G-Y, Zhang J. Bipyridinium derivative-based coordination
polymers: from synthesis to materials applications. Coord Chem Rev 2019;378:
533–60. https://doi.org/10.1016/j.ccr.2017.10.029.
[6] Hu ML, Masoomi MY, Morsali A. Template strategies with MOFs. Coord Chem Rev
2019;387:415–35. https://doi.org/10.1016/j.ccr.2019.02.021.
[7] Ovsyannikov A, Solovieva S, Antipin I, Ferlay S. Coordination polymers based on
calixarene derivatives: structures and properties. Coord Chem Rev 2017;352:
151–86. https://doi.org/10.1016/j.ccr.2017.09.004.
[8] Anderson R, Gómez-Gualdrón DA. Increasing topological diversity during computa-
tional “synthesis” of porous crystals: how and why. CrystEngComm 2019;21:
1653–65. https://doi.org/10.1039/c8ce01637b.
[9] Liu J, Wöll C. Surface-supported metal-organic framework thin films: Fabrication
methods, applications, and challenges. Chem Soc Rev 2017;46:5730–70. https://
doi.org/10.1039/c7cs00315c.
[10] Zhang T, Jin Y, Shi Y, Li M, Li J, Duan C. Modulating photoelectronic performance of
metal–organic frameworks for premium photocatalysis. Coord Chem Rev 2019;
380:201–29. https://doi.org/10.1016/j.ccr.2018.10.001.
[11] Seoane B, Castellanos S, Dikhtiarenko A, Kapteijn F, Gascon J. Multi-scale crystal en-
gineering of metal organic frameworks. Coord Chem Rev 2016;307:147–87.
https://doi.org/10.1016/j.ccr.2015.06.008.
[12] Dutta G, Jana AK, Singh DK, Eswaramoorthy M, Natarajan S. Encapsulation of silver
nanoparticles in an amine-functionalized porphyrin metal–organic framework and
its use as a heterogeneous catalyst for CO2 fixation under atmospheric pressure.
Chem - An Asian J 2018;13:2677–84. https://doi.org/10.1002/asia.201800815.
[13] Yin Z, Wan S, Yang J, Kurmoo M, Zeng MH. Recent advances in post-synthetic mod-
ification of metal–organic frameworks: new types and tandem reactions. Coord
Chem Rev 2019;378:500–12. https://doi.org/10.1016/j.ccr.2017.11.015.
[14] Nadar SS, O NV, Suresh S, Rao P, Ahirrao DJ, Adsare S. Recent progress in nanostruc-
tured magnetic framework composites (MFCs): Synthesis and applications. J
Taiwan Inst Chem Eng 2018;91:653–77. https://doi.org/10.1016/j.jtice.2018.06.
029.
[15] Garibay SJ. Functionalization of Metal-Organic Frameworks with Metalloligands
and Postsynthetic Modification. San Diego: University of California; 2011.
[16] Huang YB, Liang J, Wang XS, Cao R. Multifunctional metal-organic framework cat-
alysts: synergistic catalysis and tandem reactions. Chem Soc Rev 2017;46:126–57.
https://doi.org/10.1039/c6cs00250a.
 S.A. Younis et al. / Advances in Colloid and Interface Science 277 (2020) 102108
[17] Dzhardimalieva GI, Uflyand IE. Design and synthesis of coordination polymers with
chelated units and their application in nanomaterials science. RSC Adv 2017;7:
42242–88. https://doi.org/10.1039/c7ra05302a.
[18] Liu T, Tian J, Cui L, Liu Q, Wu L, Zhang X. Facile strategy to prepare a
metalloporphyrin-based hydrophilic porous organic polymer with enhanced
peroxidase-like activity and high stability for colorimetric detection of H 2 O 2
and glucose. Colloids Surf B: Biointerfaces 2019;178:137–45. https://doi.org/10.
1016/j.colsurfb.2019.03.008.
[19] Lin H, Wu Y, Tong S, Hu S, Li H, Pan C, et al. Assembly of covalently inorganic-
organic hybrid molecular framework based on porphyrin and phthalocyanine de-
rivatives—sensitizer for dye sensitized solar cells. Open J Inorg Chem 2018;8:
1–20. https://doi.org/10.4236/ojic.2018.81001.
[20] Zhang W, Dynes JJ, Hu Y, Jiang P, Ma S. Porous metal-metalloporphyrin gel as cat-
alytic binding pocket for highly efficient synergistic catalysis. Nat Commun 2019;
10:1–8. https://doi.org/10.1038/s41467-019-09881-9.
[21] Cook LP, Brewer G, Wong-Ng W. Structural aspects of porphyrins for functional
materials applications. Crystals 2017;7:223. https://doi.org/10.3390/cryst7070223.
[22] ichi Yamazaki S. Metalloporphyrins and related metallomacrocycles as
electrocatalysts for use in polymer electrcolyte fuel cells and water electrolyzers.
Coord Chem Rev 2018;373:148–66. https://doi.org/10.1016/j.ccr.2017.09.016.
[23] Garibay SJ, Stork JR, Cohen SM. The use of metalloligands in metal-organic frame-
works. In: Karlin KD, editor. Prog. Inorg. Chem. John Wiley & Sons, Inc; 2009.
p. 335–78. https://doi.org/10.1002/9780470440124.ch4.
[24] Pereira C, Simoes M, Tome J, Almeida Paz F. Porphyrin-based metal-organic frame-
works as heterogeneous catalysts in oxidation reactions. Molecules 2016;21:1348.
https://doi.org/10.3390/molecules21101348.
[25] Shi L, Yang L, Zhang H, Chang K, Zhao G, Kako T, et al. Implantation of Iron(III) in
porphyrinic metal organic frameworks for highly improved photocatalytic perfor-
mance. Appl Catal B Environ 2018;224:60–8. https://doi.org/10.1016/j.apcatb.
2017.10.033.
[26] Peng Y, Huang H, Zhang Y, Kang C, Chen S, Song L, et al. A versatile MOF-based trap
for heavy metal ion capture and dispersion. Nat Commun 2018;9:187. https://doi.
org/10.1038/s41467-017-02600-2.
[27] Krupitsky H, Stein Z, Goldberg I, Strouse CE. Crystalline complexes, coordination
polymers and aggregation modes of tetra (4-pyridyl) porphyrin. J Incl Phenom
Mol Recognit Chem 1994;18:177–92.
[28] Dastidar P, Stein Z, Goldberg I, Strouse CE. Supramolecular assembly of functional-
ized metalloporphyrins. Porous crystalline networks of zinc-tetra(4-
carboxyphenyl)porphyrin. Supramol Chem 1996;7:257–70. https://doi.org/10.
1080/10610279608035196.
[29] Goldberg I. Crystal engineering of porphyrin framework solids. Chem Commun
2005(10):1243–54.
[30] Zhang W, Jiang P, Wang Y, Zhang J, Zhang P. Synthesis of two metal-porphyrin
frameworks assembled from porphyrin building motifs, 5, 10, 15, 20-
tetrapyridylporphyrin and their base catalyzed property. Inorg Chem Commun
2015;61:100–4. https://doi.org/10.1016/j.inoche.2015.09.002.
[31] Shao S, Rajendiran V, Lovell JF. Metalloporphyrin nanoparticles: coordinating di-
verse theranostic functions. Coord Chem Rev 2017. https://doi.org/10.1016/j.ccr.
2017.09.002.
[32] Kitagawa S, Uemura K. Dynamic porous properties of coordination polymers in-
spired by hydrogen bonds. Chem Soc Rev 2005;34:109–19. https://doi.org/10.
1039/b313997m.
[33] Shaikh SM, Chakraborty A, Alatis J, Cai M, Danilov E, Morris AJ. Light harvesting and
energy transfer in a porphyrin-based metal organic framework. Faraday Discuss
2019. https://doi.org/10.1039/C8FD00194D.
[34] Mishra MK, Choudhary H, Cordes DB, Kelley SP, Rogers RD. Structural diversity in
tetrakis(4-pyridyl)porphyrin supramolecular building blocks. Cryst Growth Des
2019;19:3529–42. https://doi.org/10.1021/acs.cgd.9b00399.
[35] Diercks CS, Yaghi OM. The atom, the molecule, and the covalent organic frame-
work. Science (80- ) 2017;355:923. https://doi.org/10.1126/science.aal1585.
[36] Xia ZJ, Yang HC, Chen Z, Waldman RZ, Zhao Y, Zhang C, et al. Porphyrin covalent
organic framework (POF)-based interface engineering for solar steam generation.
Adv Mater Interfaces 2019;1900254:1–6. https://doi.org/10.1002/admi.
201900254.
[37] Wang H, Zeng Z, Xu P, Li L, Zeng G, Xiao R, et al. Recent progress in covalent organic
framework thin films: fabrications, applications and perspectives. Chem Soc Rev
2019;48:488–516. https://doi.org/10.1039/c8cs00376a.
[38] Lyle SJ, Waller PJ, Yaghi OM. Covalent organic frameworks: organic chemistry ex-
tended into two and three dimensions. Trends Chem 2019;1:172–84. https://doi.
org/10.1016/j.trechm.2019.03.001.
[39] Wang K, Wang T, Liu H, Qi D, Jiang J, Li Y, et al. Tetrapyrrole macrocycle based con-
jugated two-dimensional mesoporous polymers and covalent organic frameworks:
From synthesis to material applications. Coord Chem Rev 2019;378:188–206.
https://doi.org/10.1016/j.ccr.2017.08.023.
[40] Liu QY, Li JF, Wang JW. Research of covalent organic frame materials based on por-
phyrin units. J Incl Phenom Macrocycl Chem 2019;95:1–15. https://doi.org/10.
1007/s10847-019-00924-8.
[41] Liu X-H, Guan C-Z, Zheng Q-N, Wang D, Wan L-J. Molecular engineering of Schiff-
base linked covalent polymers with diverse topologies by gas-solid interface reac-
tion. J Chem Phys 2015;142:101905.
[42] Ma W, Yu P, Ohsaka T, Mao L. An efficient electrocatalyst for oxygen reduction re-
action derived from a Co-porphyrin-based covalent organic framework.
Electrochem Commun 2015;52:53–7.
[43] Hou Y, Zhang X, Wang C, Qi D, Gu Y, Wang Z, et al. Novel imine-linked porphyrin
covalent organic frameworks with good adsorption removing properties of RhB.
New J Chem 2017;41:6145–51.
47
[44] Neti VSPK, Wang J, Deng S, Echegoyen L. Selective CO 2 adsorption in a porphyrin
polymer with benzimidazole linkages. RSC Adv 2015;5:10960–3.
[45] Liao H, Wang H, Ding H, Meng X, Xu H, Wang B, et al. A 2D porous porphyrin-based
covalent organic framework for sulfur storage in lithium–sulfur batteries. J Mater
Chem A 2016;4:7416–21.
[46] Nguyen V, Grünwald M. Microscopic origins of poor crystallinity in the synthesis of
covalent organic framework COF-5. J Am Chem Soc 2018;140:3306–11. https://doi.
org/10.1021/jacs.7b12529.
[47] Chen X, Addicoat M, Irle S, Nagai A, Jiang D. Control of crystallinity and porosity of
covalent organic frameworks by managing interlayer interactions based on self-
complementary π-electronic force. J Am Chem Soc 2012;135:546–9.
[48] Shi Y, Liu S, Liu Y, Sun C, Chang M, Zhao X, et al. Facile fabrication of nanoscale
porphyrinic covalent organic polymers for combined photodynamic and
photothermal cancer therapy. ACS Appl Mater Interfaces 2019;11:12321–6.
https://doi.org/10.1021/acsami.9b00361.
[49] Liu S, Liu Y, Hu C, Zhao X, Ma P, Pang M. Boosting the antitumor efficacy over a
nanoscale porphyrin-based covalent organic polymer via synergistic photody-
namic and photothermal therapy. Chem Commun 2019;55:6269–72. https://doi.
org/10.1039/C9CC02345C.
[50] Zhang M, Zheng R, Ma Y, Chen R, Sun X, Sun X. A novel one-dimensional
porphyrin-based covalent organic framework. Molecules 2019;24:1–9. https://
doi.org/10.3390/molecules24183361.
[51] Zhang P, Hu J, Liu B, Yang J, Hou H. Recent advances in metalloporphyrins for envi-
ronmental and energy applications. Chemosphere 2019;219:617–35. https://doi.
org/10.1016/j.chemosphere.2018.12.024.
[52] Lin S, Diercks CS, Zhang Y-B, Kornienko N, Nichols EM, Zhao Y, et al. Covalent or-
ganic frameworks comprising cobalt porphyrins for catalytic CO2 reduction in
water. Science (80- ) 2015;349:1208–13.
[53] Li BQ, Zhang SY, Wang B, Xia ZJ, Tang C, Zhang Q. A porphyrin covalent organic
framework cathode for flexible Zn-air batteries. Energy Environ Sci 2018;11:
1723–9. https://doi.org/10.1039/c8ee00977e.
[54] Diercks CS, Lin S, Kornienko N, Kapustin EA, Nichols EM, Zhu C, et al. Reticular elec-
tronic tuning of porphyrin active sites in covalent organic frameworks for electro-
catalytic carbon dioxide reduction. J Am Chem Soc 2018;140:1116–22. https://doi.
org/10.1021/jacs.7b11940.
[55] Zhao M, De Wu C. Synthesis and post-metalation of a covalent-porphyrinic frame-
work for highly efficient aerobic epoxidation of olefins. Catal Commun 2017;99:
146–9. https://doi.org/10.1016/j.catcom.2017.06.001.
[56] Shinde DB, Kandambeth S, Pachfule P, Kumar RR, Banerjee R. Bifunctional covalent
organic frameworks with two dimensional organocatalytic micropores. Chem
Commun 2014;51:310–3.
[57] Cheung PL, Lee SK, Kubiak CP. Facile solvent-free synthesis of thin iron porphyrin
COFs on carbon cloth electrodes for CO2 reduction. Chem Mater 2019;31:
1908–19. https://doi.org/10.1021/acs.chemmater.8b04370.
[58] Hao W, Chen D, Li Y, Yang Z, Xing G, Li J, et al. Facile synthesis of porphyrin based
covalent organic frameworks via an A 2 B 2 monomer for highly efficient heteroge-
neous catalysis. Chem Mater 2019;31:8100–5. https://doi.org/10.1021/acs.
chemmater.9b02718.
[59] Lin G, Ding H, Chen R, Peng Z, Wang B, Wang C. 3D porphyrin-based covalent or-
ganic frameworks. J Am Chem Soc 2017;139:8705–9. https://doi.org/10.1021/
jacs.7b04141.
[60] Zuo Q, Cheng G, Luo W. A reduced graphene oxide/covalent cobalt porphyrin
framework for efficient oxygen reduction reaction. Dalton Trans 2017;46:
9344–8. https://doi.org/10.1039/c7dt01694h.
[61] Liu Y, Yan X, Li T, Zhang W-D, Fu Q-T, Lu H-S, et al. Three-dimensional
porphyrin-based covalent organic frameworks with tetrahedral building
blocks for single-site catalysis. New J Chem 2019;43:16907–14. https://doi.
org/10.1039/C9NJ04017J.
[62] Zhao H, Jin Z, Su H, Jing X, Sun F, Zhu G. Targeted synthesis of a 2D ordered porous
organic framework for drug release. Chem Commun 2011;47:6389–91. https://doi.
org/10.1039/c1cc00084e.
[63] Chedid G, Yassin A. Recent trends in covalent and metal organic frameworks for
biomedical applications. Nanomaterials 2018;8:916. https://doi.org/10.3390/
nano8110916.
[64] Bai Y, Dou Y, Xie LH, Rutledge W, Li JR, Zhou HC. Zr-based metal-organic frame-
works: design, synthesis, structure, and applications. Chem Soc Rev 2016;45:
2327–67. https://doi.org/10.1039/c5cs00837a.
[65] Luo Y, Liu J, Liu Y, Lyu Y. Porphyrin-based covalent triazine frameworks: Porosity,
adsorption performance, and drug delivery. J Polym Sci Part A Polym Chem 2017;
55:2594–600. https://doi.org/10.1002/pola.28543.
[66] Hynek J, Zelenka J, Rathouský J, Kubát P, Ruml T, Demel J, et al. Designing
porphyrinic covalent organic frameworks for the photodynamic inactivation of
bacteria. ACS Appl Mater Interfaces 2018;10:8527–35. https://doi.org/10.1021/
acsami.7b19835.
[67] Gonzalez-Nelson A, Coudert F-X, van der Veen M. Rotational dynamics of linkers in
metal–organic frameworks. Nanomaterials 2019;9:330. https://doi.org/10.3390/
nano9030330.
[68] Hoskins BF, Robson R. Design and construction of a new class of scaffolding-like
materials comprising infinite polymeric frameworks of 3D-linked molecular rods.
A reappraisal of the zinc cyanide and cadmium cyanide structures and the synthe-
sis and structure of the diamond-rela. J Am Chem Soc 1990;112:1546–54.
[69] Hoskins BF, Robson R. Infinite polymeric frameworks consisting of three dimen-
sionally linked rod-like segments. J Am Chem Soc 1989;111:5962–4.
[70] Stock N, Biswas S. Synthesis of metal-organic frameworks ( MOFs ): routes to var-
ious MOF topologies, morphologies, and composites. Chem Rev 2012;112:933–69.
https://doi.org/10.1021/cr200304e.
48 S.A. Younis et al. / Advances in Colloid and Interface Science 277 (2020) 102108
[71] Yaghi OM, Li G, Li H. Selective binding and removal of guests in a microporous
metal–organic framework. Nature 1995;378:703.
[72] Yaghi OM, Li H. Hydrothermal synthesis of a metal-organic framework containing
large rectangular channels. J Am Chem Soc 1995;117:10401–2.
[73] Kondo M, Yoshitomi T, Matsuzaka H, Kitagawa S, Seki K. Three-dimensional frame-
work with channeling cavities for small molecules: {[M2(4, 4′-bpy)3(NO3)
4]·xH2O}n (M = Co, Ni, Zn). Angew Chem Int Ed 1997;36:1725–7.
[74] Tian Y, Cai C, Ji Y, You X, Peng S, Lee G. [Co5 (im) 10· 2 MB]∞: A metal-organic
open-framework with zeolite-like topology. Angew Chem 2002;114:1442–4.
[75] Park KS, Ni Z, Côté AP, Choi JY, Huang R, Uribe-Romo FJ, et al. Exceptional chemical
and thermal stability of zeolitic imidazolate frameworks. Proc Natl Acad Sci U S A
2006;103:10186–91. https://doi.org/10.1073/pnas.0602439103.
[76] Zhang Y, Yang X, Zhou HC. Synthesis of MOFs for heterogeneous catalysis via linker
design. Polyhedron 2018;154:189–201. https://doi.org/10.1016/j.poly.2018.07.021.
[77] Qin JS, Yuan S, Wang Q, Alsalme A, Zhou HC. Mixed-linker strategy for the con-
struction of multifunctional metal-organic frameworks. J Mater Chem A 2017;5:
4280–91. https://doi.org/10.1039/c6ta10281f.
[78] Jiao J, Gong W, Wu X, Yang S, Cui Y. Multivariate crystalline porous materials: syn-
thesis, property and potential application. Coord Chem Rev 2019;385:174–90.
https://doi.org/10.1016/j.ccr.2019.01.016.
[79] Huh S, Kim SJ, Kim Y. Porphyrinic metal-organic frameworks from custom-
designed porphyrins. CrystEngComm 2016;18:345–68. https://doi.org/10.1039/
c5ce02106e.
[80] An H, Li M, Gao J, Zhang Z, Ma S, Chen Y. Incorporation of biomolecules in Metal-
Organic Frameworks for advanced applications. Coord Chem Rev 2019;384:
90–106. https://doi.org/10.1016/j.ccr.2019.01.001.
[81] Pang Q, Tu B, Li Q. Metal–organic frameworks with multicomponents in order.
Coord Chem Rev 2019;388:107–25. https://doi.org/10.1016/j.ccr.2019.02.022.
[82] Giménez-Marqués M, Hidalgo T, Serre C, Horcajada P. Nanostructured metal–
organic frameworks and their bio-related applications. Coord Chem Rev 2016;
307:342–60. https://doi.org/10.1016/j.ccr.2015.08.008.
[83] Kumar P, Vellingiri K, Kim KH, Brown RJC, Manos MJ. Modern progress in metal-
organic frameworks and their composites for diverse applications. Microporous
Mesoporous Mater 2017;253:251–65. https://doi.org/10.1016/j.micromeso.2017.
07.003.
[84] Cai H, Huang Y-L, Li D. Biological metal–organic frameworks: Structures, host–
guest chemistry and bio-applications. Coord Chem Rev 2019;378:207–21.
https://doi.org/10.1016/j.ccr.2017.12.003.
[85] Li N, Feng R, Zhu J, Chang Z, Bu X, et al. Coord Chem Rev 2018. https://doi.org/10.
1016/j.ccr.2018.05.016 xxx:xxx–xxx.
[86] Chakraborty J, Nath I, Verpoort F. Snapshots of encapsulated porphyrins and heme
enzymes in metal-organic materials: A prevailing paradigm of heme mimicry.
Coord Chem Rev 2016;326:135–63. https://doi.org/10.1016/j.ccr.2016.08.006.
[87] Lin G, Ding H, Yuan D, Wang B, Wang C. A pyrene-based, fluorescent three-
dimensional covalent organic framework. J Am Chem Soc 2016;138:3302–5.
[88] Lee CY, Farha OK, Hong BJ, Sarjeant AA, Nguyen ST, Hupp JT. Light-harvesting
metal–organic frameworks (MOFs): efficient strut-to-strut energy transfer in
bodipy and porphyrin-based MOFs. J Am Chem Soc 2011;133:15858–61.
[89] Li B, Chrzanowski M, Zhang Y, Ma S. Applications of metal-organic frameworks fea-
turing multi-functional sites. Coord Chem Rev 2015;307:106–29. https://doi.org/
10.1016/j.ccr.2015.05.005.
[90] Lin W, Hu Q, Jiang K, Yang Y, Yang Y, Cui Y, et al. A porphyrin-based metal-organic
framework as a pH-responsive drug carrier. J Solid State Chem 2016;237:307–12.
https://doi.org/10.1016/j.jssc.2016.02.040.
[91] Vogel E, Köcher M, Schmickler H, Lex J. Porphycene—a novel porphin isomer.
Angew Chem Int Ed Eng 1986;25:257–9.
[92] Abánades Lázaro I, Forgan RS. Application of zirconium MOFs in drug delivery and
biomedicine. Coord Chem Rev 2019;380:230–59. https://doi.org/10.1016/j.ccr.
2018.09.009.
[93] Vogel E. Porphyrinoid macrocycles: A cornucopia of novel chromophores. Pure
Appl Chem 1996;68:1355–60.
[94] Lash TD, Lammer AD, Ferrence GM. Neo-confused porphyrins, a new class of por-
phyrin isomers. Angew Chem Int Ed 2011;50:9718–21. https://doi.org/10.1002/
anie.201104826.
[95] Punnagai M, Joseph S, Sastry GN. A theoretical study of porphyrin isomers and their
core-modified analogues : cis-trans isomerism , tautomerism and relative stabili-
ties. J Chem Sci 2004;116:271–83.
[96] Gao R, Liu Q, Wang J, Liu J, Yang W, Gao Z, et al. Construction of superhydrophobic
and superoleophilic nickel foam for separation of water and oil mixture. Appl Surf
Sci 2014;289:417–24. https://doi.org/10.1016/j.apsusc.2013.10.178.
[97] Zha Q, Rui X, Wei T, Xie Y. Recent advances in the design strategies for porphyrin-
based coordination polymers. CrystEngComm 2014;16:7371–84.
[98] Furuta H, Asano T, Ogawa T. “N-confused porphyrin”: A new isomer of
tetraphenylporphyrin. J Am Chem Soc 1994;116:767–8. https://doi.org/10.1021/
ja00081a047.
[99] Day NU, Wamser CC, Walter MG. Porphyrin polymers and organic frameworks.
Polym Int 2015;64:833–57. https://doi.org/10.1002/pi.4908.
[100] Ferreira GC. Handbook of Porphyrin Science-with Applications to Chemistry, Phys-
ics, Materials Science, Engineering, Biology and Medicine. , 26–30New Jersey, USA:
World Scientific Publishing Co. Pte. Ltd. All; 2014. https://doi.org/10.1142/
9789814322386.
[101] Zheng K, Ngo PD, Owens VL, Yang X, Mansoorabadi SO. The biosynthetic pathway
of coenzyme F430 in methanogenic and methanotrophic archaea. Science (80- )
2016;354:339–42.
[102] Allen LH. How common is vitamin B-12 deficiency? Am J Clin Nutr 2008;89:
693S–6S.
[103] Nakagaki S, Ferreira G, Ucoski G, Dias de Freitas Castro K. Chemical reactions cata-
lyzed by metalloporphyrin-based metal-organic frameworks. Molecules 2013;18:
7279–308. https://doi.org/10.3390/molecules18067279.
[104] Healy C, Schmitt W. Multicomponent halide templating: the effect of structure-
directing agents on the assembly of molecular and extended coordination com-
pounds. Coord Chem Rev 2018;371:67–85. https://doi.org/10.1016/j.ccr.2018.05.
014.
[105] Chen K, Wu C-D. Designed fabrication of biomimetic metal–organic frameworks for
catalytic applications. Coord Chem Rev 2019;378:445–65. https://doi.org/10.1016/
j.ccr.2018.01.016.
[106] Cuesta L, Sessler JL. π-Metal complexes of tetrapyrrolic systems. A novel coordina-
tion mode in “porphyrin-like” chemistry. Chem Soc Rev 2009;38:2716. https://doi.
org/10.1039/b905850h.
[107] Shao S, Rajendiran V, Lovell JF. Metalloporphyrin nanoparticles: coordinating di-
verse theranostic functions. Coord Chem Rev 2019;379:99–120. https://doi.org/
10.1016/j.ccr.2017.09.002.
[108] Williams RJP. The properties of metalloporphyrins. Chem Rev 1956;56:299–328.
https://doi.org/10.1021/cr50008a004.
[109] Brothers PJ. Recent developments in the coordination chemistry of porphyrin com-
plexes containing non-metallic and semi-metallic elements. J Porphyrins Phthalo-
cyanines 2002;06:259–67. https://doi.org/10.1142/S1088424602000294.
[110] Scheldt WR. Trends in metalloporphyrin stereochemistry. Acc Chem Res 1977;10:
339–45. https://doi.org/10.1021/ar50117a005.
[111] Kadish KM, Smith KM, Guilard R. The Porphyrin Handbook. San Diego: Academic
Press; 2000.
[112] Aviv-Harel I, Gross Z. Coordination chemistry of corroles with focus on main group
elements. Coord Chem Rev 2011;255:717–36. https://doi.org/10.1016/j.ccr.2010.
09.013.
[113] Brewster JT, Zafar H, Root HD, Thiabaud GD, Sessler JL. Porphyrinoid f-element
complexes. Inorg Chem 2019;59:32–47. https://doi.org/10.1021/acs.inorgchem.
9b00884.
[114] Wickramasinghe A, Jaquinod L, Nurco DJ, Smith KM. Investigations on the directive
effects of a single meso-substituent via nitration of 5, 12, 13, 17, 18-
pentasubstituted porphyrins: syntheses of conjugated β-nitroporphyrins. Tetrahe-
dron 2001;57:4261–9.
[115] Ali H, van Lier JE. Phenylselenyl halides: Efficient reagents for the selective haloge-
nation and nitration of porphyrins. Tetrahedron Lett 1991;32:5015–8.
[116] Turk H, Ford WT. Epoxidation of styrene with aqueous hypochlorite catalyzed by a
manganese (III) porphyrin bound to colloidal anion-exchange particles. J
Organomet Chem 1991;56:1253–60.
[117] Brantley SE, Gerlach B, Olmstead MM, Smith KM. Vinyl group protection in porphy-
rins and chlorins: organoselenium derivatives. Tetrahedron Lett 1997;38:937–40.
[118] Kvíčala J, Beneš M, Paleta O, Král V. Regiospecific nucleophilic substitution in 2, 3, 4,
5, 6-pentafluorobiphenyl as model compound for supramolecular systems. Theo-
retical study of transition states and energy profiles, evidence for tetrahedral SN2
mechanism. J Fluor Chem 2010;131:1327–37.
[119] Knör G. Spontaneous nucleophilic addition of hydroxide ions to the meso-position
of high-valent antimony-oxo porphyrin complexes. J Inorg Biochem 2001;84:
297–9.
[120] Kadish KM, Han BC, Franzen MM. Araullo-McAdams C. Syntheses and spectro-
scopic characterization of (T (p-Me2N) F4PP) H2 and (T (p-Me2N) F4PP) M
where T (p-Me2N) F4PP= the dianion of meso-tetrakis (o, o, m, m-tetrafluoro-
p-(dimethylamino) phenyl) porphyrin and M= cobalt (II), copper (II), or nickel
(II). J Am Chem Soc 1990;112:8364–8.
[121] Jiménez-Osés G, García JI, Silva AMG, Santos ARN, Tomé AC, Neves M, et al. Mech-
anistic insights on the site selectivity in successive 1, 3-dipolar cycloadditions to
meso-tetraarylporphyrins. Tetrahedron 2008;64:7937–43.
[122] Dolphin D, Traylor TG, Xie LY. Polyhaloporphyrins: unusual ligands for metals and
metal-catalyzed oxidations. Acc Chem Res 1997;30:251–9.
[123] Groves JT, Nemo TE, Myers RS. Hydroxylation and epoxidation catalyzed by iron-
porphine complexes. Oxygen transfer from iodosylbenzene. J Am Chem Soc
1979;101:1032–3.
[124] Doro FG, Smith JRL, Ferreira AG, Assis MD. Oxidation of alkanes and alkenes by
iodosylbenzene and hydrogen peroxide catalysed by halogenated manganese por-
phyrins in homogeneous solution and covalently bound to silica. J Mol Catal A
Chem 2000;164:97–108.
[125] CarvalhoDa-Silva D, Mac Leod TCO, De Faria AL, Dos Santos JS, Dai de Carvalho
MEM, Rebouças JS, et al. Carbamazepine oxidation catalyzed by manganese por-
phyrins: effects of the β-bromination of the macrocycle and the choice of oxidant.
Appl Catal A Gen 2011;408:25–30.
[126] Guedes AA, Smith JRL, Nascimento OR, Guedes DFC, Assis M das D. Catalytic activity
of halogenated iron porphyrins in alkene and alkane oxidations by iodosylbenzene
and hydrogen peroxide. J Braz Chem Soc 2005;16:835–43.
[127] da Silva DC, DeFreitas-Silva G, do Nascimento E, Rebouças JS, Barbeira PJS, Dai de
Carvalho MEM, et al. Spectral, electrochemical, and catalytic properties of a homol-
ogous series of manganese porphyrins as cytochrome P450 model: the effect of the
degree of β-bromination. J Inorg Biochem 2008;102:1932–41.
[128] Tian J, Zhang W. Synthesis, self-assembly and applications of functional polymers
based on porphyrins. Prog Polym Sci 2019;95:65–117. https://doi.org/10.1016/j.
progpolymsci.2019.05.002.
[129] Gao W-YY, Chrzanowski M, Ma S. Metal–metalloporphyrin frameworks: a resurg-
ing class of functional materials. Chem Soc Rev 2014;43:5841–66. https://doi.org/
10.1039/c4cs00001c.
[130] Yang D, Gates BC. Catalysis by metal organic frameworks: perspective and sugges-
tions for future research. ACS Catal 2019;9:1779–98. https://doi.org/10.1021/
acscatal.8b04515.
 S.A. Younis et al. / Advances in Colloid and Interface Science 277 (2020) 102108
[131] Huang X, Nakanishi K, Berova N. Porphyrins and metalloporphyrins: versatile cir-
cular dichroic reporter groups for structural studies. Chirality 2000;12:237–55.
https://doi.org/10.1002/(SICI)1520-636X(2000)12:4b237::AID-CHIR10N3.0.CO;2-
6.
[132] Lee H, Hong KI, Jang WD. Design and applications of molecular probes containing
porphyrin derivatives. Coord Chem Rev 2018;354:46–73. https://doi.org/10.1016/
j.ccr.2017.06.008.
[133] Shen R, Zhu W, Yan X, Li T, Liu Y, Li Y, et al. A porphyrin porous organic polymer
with bicatalytic sites for highly efficient one-pot tandem catalysis. Chem Commun
2019;55:822–5. https://doi.org/10.1039/c8cc08918c.
[134] Li C, Mizuno N, Yamaguchi K, Suzuki K. Self-assembly of anionic polyoxometalate-
organic architectures based on lacunary phosphomolybdates and pyridyl ligands. J
Am Chem Soc 2019;141:7687–92. https://doi.org/10.1021/jacs.9b02541.
[135] Lipstman S, Goldberg I. 2D and 3D coordination networks of tetra
(carboxyphenyl)-porphyrins with cerium and thulium ions. J Mol Struct 2008;
890:101–6.
[136] Lipstman S, Goldberg I. New cyclic tetrameric and square-grid polymeric modes of
supramolecular self-assembly of zinc tetra (4-pyridyl) porphyrin. CrystEngComm
2010;12:52–4. https://doi.org/10.1039/b914799c.
[137] Lipstman S, Goldberg I. Supramolecular crystal chemistry with porphyrin tinker-
toys. hydrogen-bonding and coordination networks with the “chair” and “table”
conformers of tetra (3-carboxyphenyl) porphyrin. Cryst Growth Des 2013;13:
942–52.
[138] Diskin-Posner Y, Dahal S, Goldberg I, Desimone JM, Diskin-posner Y, Dahal S, et al.
Crystal engineering of metalloporphyrin zeolite analogues. Angew Chem 2000;
112:1344–8.
[139] Diskin-Posner Y, Goldberg I. Porphyrin sieves. Designing open networks of tetra
(carboxyphenyl) porphyrins by extended coordination through sodium ion auxil-
iaries. New J Chem 2001;25:899–904.
[140] Shmilovits M, Diskin-Posner Y, Vinodu M, Goldberg I. Crystal engineering of “por-
phyrin sieves” based on coordination polymers of Pd-and Pt-tetra (4-
carboxyphenyl) porphyrin. Cryst Growth Des 2003;3:855–63.
[141] Shmilovits M, Vinodu M, Goldberg I. Coordination polymers of tetra (4-
carboxyphenyl) porphyrins sustained by tetrahedral zinc ion linkers. Cryst Growth
Des 2004;4:633–8.
[142] Vinodu M, Goldberg I. Complexes of hexamethylenetetramine with zinc-
tetraarylporphyrins, and their assembly modes in crystals as clathrates and
hydrogen-bonding network polymers. New J Chem 2004;28:1250–4.
[143] George S, Lipstman S, Muniappan S, Goldberg I. Porphyrin network solids: exam-
ples of supramolecular isomerism, noncentrosymmetric architectures and compet-
ing solvation. CrystEngComm 2006;8:417–24.
[144] Lipstman S, Muniappan S, George S, Goldberg I. Framework coordination polymers
of tetra (4-carboxyphenyl) porphyrin and lanthanide ions in crystalline solids. Dal-
ton Trans 2007(30):3273–81.
[145] Choi E-Y, Barron PM, Novotney RW, Hu C, Kwon Y-U, Choe W. A mixed-linker por-
phyrin framework with CdI 2-type topology. CrystEngComm 2008;10:824–6.
[146] Burnett BJ, Choe W. Sequential self-assembly in metal–organic frameworks. Dalton
Trans 2012;41:3889–94.
[147] Burnett BJ, Barron PM, Choe W. Recent advances in porphyrinic metal–organic
frameworks: materials design, synthetic strategies, and emerging applications.
CrystEngComm 2012;14:3839–46.
[148] Chung H, Barron PM, Novotny RW, Son H-T, Hu C, Choe W. Structural variation in
porphyrin pillared homologous series: influence of distinct coordination centers for
pillars on framework topology. Cryst Growth Des 2009;9:3327–32.
[149] Burnett BJ, Choe W. Stepwise pillar insertion into metal–organic frameworks: a se-
quential self-assembly approach. CrystEngComm 2012;14:6129–31.
[150] DeVries LD, Barron PM, Hurley EP, Hu C, Choe W. “Nanoscale lattice fence” in a
metal–organic framework: interplay between hinged topology and highly aniso-
tropic thermal response. J Am Chem Soc 2011;133:14848–51.
[151] Burnett BJ, Barron PM, Hu C, Choe W. Stepwise synthesis of metal–organic
frameworks: replacement of structural organic linkers. J Am Chem Soc 2011;
133:9984–7.
[152] Barron PM, Wray CA, Hu C, Guo Z, Choe W. A bioinspired synthetic approach for
building metal− organic frameworks with accessible metal centers. Inorg Chem
2010;49:10217–9.
[153] Choi E-Y, DeVries LD, Novotny RW, Hu C, Choe W. An interdigitated
metalloporphyrin framework: two-dimensional tessellation, framework flexibility,
and selective guest accommodation. Cryst Growth Des 2009;10:171–6.
[154] Verduzco JM, Chung H, Hu C, Choe W. Metal− organic framework assembled from
T-shaped and octahedral nodes: a mixed-linker strategy to create a rare anatase
TiO2 topology. Inorg Chem 2009;48:9060–2.
[155] DeVries LD, Choe W. Classification of structural motifs in porphyrinic coordination
polymers assembled from porphyrin building units, 5, 10, 15, 20-
tetrapyridylporphyrin and its derivatives. J Chem Crystallogr 2009;39:229–40.
[156] Barron PM, Son H-T, Hu C, Choe W. Highly tunable heterometallic frameworks con-
structed from paddle-wheel units and metalloporphyrins. Cryst Growth Des 2009;
9:1960–5.
[157] Suslick KS, Bhyrappa P, Chou J-H, Kosal ME, Nakagaki S, Smithenry DW, et al. Mi-
croporous porphyrin solids. Acc Chem Res 2005;38:283–91.
[158] Smithenry DW, Wilson SR, Suslick KS. A robust microporous zinc porphyrin frame-
work solid. Inorg Chem 2003;42:7719–21.
[159] Kosal ME, Chou J-HH, Wilson SR, Suslick KS. A functional zeolite analogue assem-
bled from metalloporphyrins. Nat Mater 2002;1:118. https://doi.org/10.1038/
nmat730.
[160] Kosal ME, Chou J-H, Suslick KS. A calcium-bridged porphyrin coordination network.
J Porphyrins Phthalocyanines 2002;6:377–81.
49
[161] Kosal ME, Suslick KS. Microporous porphyrin and metalloporphyrin materials. J
Solid State Chem 2000;152:87–98.
[162] Shultz AM, Farha OK, Hupp JT, Nguyen ST. A catalytically active, permanently mi-
croporous MOF with metalloporphyrin struts. J Am Chem Soc 2009;131:4204–5.
https://doi.org/10.1021/ja900203f.
[163] Farha OK, Shultz AM, Sarjeant AA, Nguyen ST, Hupp JT. Active-site-accessible,
Porphyrinic metal− organic framework materials. J Am Chem Soc 2011;133:
5652–5.
[164] Jin S, Son H-J, Farha OK, Wiederrecht GP, Hupp JT. Energy transfer from quantum
dots to metal–organic frameworks for enhanced light harvesting. J Am Chem Soc
2013;135:955–8.
[165] So MC, Jin S, Son H-J, Wiederrecht GP, Farha OK, Hupp JT. Layer-by-layer fabrication
of oriented porous thin films based on porphyrin-containing metal–organic frame-
works. J Am Chem Soc 2013;135:15698–701.
[166] Son H-J, Jin S, Patwardhan S, Wezenberg SJ, Jeong NC, So M, et al. Light-harvesting
and ultrafast energy migration in porphyrin-based metal–organic frameworks. J
Am Chem Soc 2013;135:862–9.
[167] Takaishi S, DeMarco EJ, Pellin MJ, Farha OK, Hupp JT. Solvent-assisted linker ex-
change (SALE) and post-assembly metallation in porphyrinic metal-organic frame-
work materials. Chem Sci 2013;4:1509–13. https://doi.org/10.1039/c2sc21516k.
[168] Abrahams BF, Hoskins BF, Robson R. A new type of infinite 3D polymeric network
containing 4-connected, peripherally-linked metalloporphyrin building blocks. J
Am Chem Soc 1991;113:3606–7.
[169] Lin K. SMTP-1: the first functionalized metalloporphyrin molecular sieves with
large channels. Angew Chem Int Ed 1999;38:2730–2.
[170] Wang X-S, Meng L, Cheng Q, Kim C, Wojtas L, Chrzanowski M, et al. Three-
dimensional porous metal–metalloporphyrin framework consisting of nanoscopic
polyhedral cages. J Am Chem Soc 2011;133:16322–5.
[171] Sen Wang X-S, Chrzanowski M, Kim C, Gao W-YY, Wojtas L, Chen Y-SS, et al. Quest
for highly porous metal–metalloporphyrin framework based upon a custom-
designed octatopic porphyrin ligand. Chem Commun 2012;48:7173–5. https://
doi.org/10.1039/c2cc33118g.
[172] Sen Wang X-S, Chrzanowski M, Gao W-YY, Wojtas L, Chen Y-SS, Zaworotko MJ,
et al. Vertex-directed self-assembly of a high symmetry supermolecular building
block using a custom-designed porphyrin. Chem Sci 2012;3:2823–7. https://doi.
org/10.1039/c2sc20330h.
[173] Wang X, Chrzanowski M, Wojtas L, Chen Y, Ma S. Formation of a metalloporphyrin-
based nanoreactor by postsynthetic metal–ion exchange of a polyhedral-cage con-
taining a metal–metalloporphyrin framework. Chem Eur J 2013;19:3297–301.
[174] Choi E-Y, Barron PM, Novotny RW, Son H-T, Hu C, Choe W. Pillared porphyrin ho-
mologous series: intergrowth in metal− organic frameworks. Inorg Chem 2008;
48:426–8.
[175] Meng L, Cheng Q, Kim C, Gao WY, Wojtas L, Chen YS, et al. Crystal engineering of a
microporous, catalytically active fcu topology MOF using a custom-designed
metalloporphyrin linker. Angew Chem Int Ed 2012;51:10082–5. https://doi.org/
10.1002/anie.201205603.
[176] Chen Y, Hoang T, Ma S. Biomimetic catalysis of a porous iron-based metal–
metalloporphyrin framework. Inorg Chem 2012;51:12600–2.
[177] Guo Z, Chen B. Recent developments in metal-metalloporphyrin frameworks. Dal-
ton Trans 2015;44:14574–83. https://doi.org/10.1039/c5dt02170g.
[178] Liu J, Chen L, Cui H, Zhang J, Zhang L, Su C-Y. Applications of metal – organic frame-
works in heterogeneous supramolecular catalysis. Chem Soc Rev 2014;43:
6011–61. https://doi.org/10.1039/c4cs00094c.
[179] Chino M, Leone L, Zambrano G, Pirro F, D’Alonzo D, Firpo V, et al. Oxidation catalysis
by iron and manganese porphyrins within enzyme-like cages. Biopolymers 2018;
109:e23107. https://doi.org/10.1002/bip.23107.
[180] Gao W, Chrzanowski M, Ma S. Metal – metalloporphyrin frameworks : a resurging
class of functional materials. Chem Soc Rev 2014;43:5841–66. https://doi.org/10.
1039/c4cs00001c.
[181] Beyzavi MH, Vermeulen NA, Zhang K, So M, Kung CW, Hupp JT, et al. Liquid-phase
epitaxially grown metal–organic framework thin films for efficient tandem cataly-
sis through site-isolation of catalytic centers. Chempluschem 2016;81:708–13.
https://doi.org/10.1002/cplu.201600046.
[182] He L, Nath JK, Lin Q. Robust multivariate metal-porphyrin frameworks for efficient
ambient fixation of CO 2 to cyclic carbonates. Chem Commun 2019;55:412–5.
https://doi.org/10.1039/c8cc07865c.
[183] Choi E-Y, Wray CA, Hu C, Choe W. Highly tunable metal–organic frameworks with
open metal centers. CrystEngComm 2009;11:553–5.
[184] Choi EY, Wray CA, Hu C, Choe W. Highly tunable metal-organic frameworks with
open metal centers. CrystEngComm 2009;11:553–5. https://doi.org/10.1039/
b819707p.
[185] Gordillo MA, Panda DK, Saha S. Efficient MOF-sensitized solar cells featuring
solvothermally grown [100]-oriented pillared porphyrin framework-11 films on
ZnO/FTO surfaces. ACS Appl Mater Interfaces 2019;11:3196–206. https://doi.org/
10.1021/acsami.8b17807.
[186] Kandambeth S, Shinde DB, Panda MK, Lukose B, Heine T, Banerjee R. Enhancement
of chemical stability and crystallinity in porphyrin-containing covalent organic
frameworks by intramolecular hydrogen bonds. Angew Chem Int Ed 2013;52:
13052–6. https://doi.org/10.1002/anie.201306775.
[187] Meng S, Ma H, Jiang L, Ren H, Zhu G. A facile approach to prepare porphyrinic po-
rous aromatic frameworks for small hydrocarbon separation. J Mater Chem A 2014;
2:14536–41. https://doi.org/10.1039/c4ta00984c.
[188] Chen J, Zhang J, Zhu D, Li T. One-pot synthesized porphyrin-based polymer sup-
ported gold nanoparticles as efficient catalysts for alkyne hydration and alcohol ox-
idation in water. Gold Bull 2019;52:19–26. https://doi.org/10.1007/s13404-018-
0249-9.
50 S.A. Younis et al. / Advances in Colloid and Interface Science 277 (2020) 102108
[189] Wang Z, Yuan S, Mason A, Reprogle B, Liu D-J, Yu L. Nanoporous porphyrin poly-
mers for gas storage and separation. Macromolecules 2012;45:7413–9.
[190] O’Keeffe M, Peskov MA, Ramsden SJ, Yaghi OM, O’Keeffe M, Peskov MA, et al. The
reticular chemistry structure resource (RCSR) database of, and symbols for, crystal
nets. Acc Chem Res 2008;41:1782–9. https://doi.org/10.1021/ar800124u.
[191] Kadish KM, Smith KM, Guilard R, editors. The Porphyrin Handbook: Volume 20 /
Phthalocyanines: Structural Characterization. San Diego, California, USA: Academic
Press; 2003.
[192] Koposova EA, Ermolenko YE, Offenhäusser A, Mourzina YG. Self-assembly and pho-
toconductivity of binary porphyrin nanostructures of meso-tetrakis(4-
sulfonatophenyl)porphine and Co(III) meso-tetra(4-pyridyl)porphine chloride.
Colloids Surfaces A Physicochem Eng Asp 2018;548:172–8. https://doi.org/10.
1016/j.colsurfa.2018.03.053.
[193] La DD, Thi HPN, Kim YS, Rananaware A, Bhosale SV. Facile fabrication of Cu(II)-por-
phyrin MOF thin films from tetrakis(4-carboxyphenyl)porphyrin and Cu(OH)2
nanoneedle array. Appl Surf Sci 2017;424:145–50. https://doi.org/10.1016/j.
apsusc.2017.01.110.
[194] Liu J, Bo X, Li M, Yin D, Guo L. Contrastive study on porphyrinic iron metal-
organic framework supported on various carbon matrices as efficient
electrocatalysts. J Colloid Interface Sci 2018;513:438–47. https://doi.org/10.
1016/j.jcis.2017.11.028.
[195] Tong XL, Lin HL, Xin JH, Liu F, Li M, Zhu XP. Recent advances as materials of func-
tional metal-organic frameworks. J Nanomater 2013;2013. https://doi.org/10.
1155/2013/616501.
[196] zhou Li Y, Z hua Fu, Xu G. Metal-organic framework nanosheets: Preparation and
applications. Coord Chem Rev 2019;388:79–106. https://doi.org/10.1016/j.ccr.
2019.02.033.
[197] Zhang M, Gu ZY, Bosch M, Perry Z, Zhou HC. Biomimicry in metal-organic ma-
terials. Coord Chem Rev 2015;293–294:327–56. https://doi.org/10.1016/j.ccr.
2014.05.031.
[198] Tripuramallu BK, Goswami S, Goldberg I. Open MOFs with unique hexatopic zinc-
5,15-bis(4′-carboxyphenyl)-10,20-bis(3′,5′-dicarboxyphenyl)porphyrin linker.
Cryst Growth Des 2018;18:230–41. https://doi.org/10.1021/acs.cgd.7b01171.
[199] Hou Y, Liu L, Zhang Z, Sun J, Zhang Y, Jiang J. Synthesis, crystal structures, and fluo-
rescence properties of porphyrin alkaline earth MOFs. Inorg Chem Commun 2018;
95:36–9. https://doi.org/10.1016/j.inoche.2018.07.005.
[200] Leng F, Liu H, Ding M, Lin QP, Jiang HL. Boosting photocatalytic hydrogen produc-
tion of c MOFs: the metal location in metalloporphyrin matters. ACS Catal 2018;
8:4583–90. https://doi.org/10.1021/acscatal.8b00764.
[201] Wang X-N, Li J-L, Zhao Y-M, Pang J, Li B, Zhang T-L, et al. Structural tuning of zinc–
porphyrin frameworks via auxiliary nitrogen-containing ligands towards selective
adsorption of cationic dyes. Chem Commun 2019;55:6527–30. https://doi.org/10.
1039/C9CC02405K.
[202] Diskin-Posner Y, Dahal S, Goldberg I. New effective synthons for supramolecular
self-assembly of meso-carboxyphenylporphyrins. Chem Commun 2000(7):585–6.
[203] Kempe R. Coordination polymers that contain accessible metal centres-synthesis
and structure of a nickel cluster connected porphyrin network. Zeitschrift Für
Anorg Und Allg Chemie 2005;631:1038–40.
[204] Zou C, Wu C-D. Functional porphyrinic metal–organic frameworks: crystal engi-
neering and applications. Dalton Trans 2012;41:3879–88. https://doi.org/10.
1039/c2dt11989g.
[205] Bai Y, Dou Y, Xie L, Rutledge W, Li J, Zhou H. Zr-based metal–organic frameworks:
design, synthesis, structure, and applications. Chem Soc Rev 2016;45:2327–67.
https://doi.org/10.1039/C5CS00837A.
[206] Kim M, Cohen SM. Discovery, development, and functionalization of Zr(iv)-based
metal-organic frameworks. CrystEngComm 2012;14:4096–104. https://doi.org/
10.1039/c2ce06491j.
[207] Feng D, Jiang H, Chen Y, Gu Z, Wei Z, Zhou H-C. Metal–organic frameworks based
on previously unknown Zr 8 /Hf 8 cubic clusters. Inorg Chem 2013;52:12661–7.
https://doi.org/10.1021/ic4018536.
[208] Feng D, Gu ZY, Chen YP, Park J, Wei Z, Sun Y, et al. A highly stable porphyrinic zir-
conium metal-organic framework with shp-a topology. J Am Chem Soc 2014;136:
17714–7. https://doi.org/10.1021/ja510525s.
[209] Bon V, Senkovska I, Baburin IA, Kaskel S. Zr-and Hf-based metal–organic frame-
works: tracking down the polymorphism. Cryst Growth Des 2013;13:1231–7.
[210] Feng D, Gu Z, Li J, Jiang H, Wei Z, Zhou H. Zirconium-metalloporphyrin PCN-222:
mesoporous metal–organic frameworks with ultrahigh stability as biomimetic cat-
alysts. Angew Chem 2012;124:10453–6.
[211] Jiang H-L, Feng D, Wang K, Gu Z-Y, Wei Z, Chen Y-P, et al. An exceptionally stable,
porphyrinic Zr metal–organic framework exhibiting pH-dependent fluorescence. J
Am Chem Soc 2013;135:13934–8.
[212] Feng D, Chung WC, Wei Z, Gu ZY, Jiang HL, Chen YP, et al. Construction of
ultrastable porphyrin Zr metal-organic frameworks through linker elimination. J
Am Chem Soc 2013;135:17105–10. https://doi.org/10.1021/ja408084j.
[213] Feng D, Wang K, Su J, Liu TF, Park J, Wei Z, et al. A highly stable zeotype mesoporous
zirconium metal-organic framework with ultralarge pores. Angew Chem Int Ed
2015;54:149–54. https://doi.org/10.1002/anie.201409334.
[214] Feng D, Jiang H-L, Chen Y-P, Gu Z-Y, Wei Z, Zhou H-C. Metal–organic frameworks
based on previously unknown Zr8/Hf8 cubic clusters. Inorg Chem 2013;52:12661–7.
[215] Gomez-Gualdron DA, Gutov OV, Krungleviciute V, Borah B, Mondloch JE, Hupp JT,
et al. Computational design of metal-organic frameworks based on stable zirco-
nium building units for storage and delivery of methane. Chem Mater 2014;26:
5632–9. https://doi.org/10.1021/cm502304e.
[216] Fateeva A, Clarisse J, Pilet G, Grenèche J-M, Nouar F, Abeykoon BK, et al. Iron and
porphyrin metal–organic frameworks: insight into structural diversity, stability,
and porosity. Cryst Growth Des 2015;15:1819–26.
[217] Abrahams BF, Hoskins BF, Michail DM, Robson R. Assembly of porphyrin building
blocks into network structures with large channels. Nature 1994;369:727.
[218] Ring DJ, Aragoni MC, Champness NR. Wilson C. A coordination polymer supramo-
lecular isomer formed from a single building block: an unexpected porphyrin rib-
bon constructed from zinctetra4-pyridylporphy. CrystEngComm 2005;7:621
10.1039 b515083n.
[219] Xie M-H, Yang X-L, Zou C, Wu C-D. A SnIV–porphyrin-based metal–organic frame-
work for the selective photo-oxygenation of phenol and sulfides. Inorg Chem 2011;
50:5318–20.
[220] Tranchemontagne DJ, Ni Z, O’Keeffe M, Yaghi OM. Reticular chemistry of metal-
organic polyhedra. Angew Chem Int Ed 2008;47:5136–47. https://doi.org/10.
1002/anie.200705008.
[221] Hagrman D, Hagrman PJ, Zubieta J. Solid-state coordination chemistry: the self-
assembly of microporous organic - inorganic hybrid frameworks constructed
from tetrapyridylporphyrin and bimetallic oxide chains or oxide clusters. Angew
Chem Int Ed 1999;38:3165–8. https://doi.org/10.1002/(SICI)1521-3773
(19991102)38:21b3165::AID-ANIE3165N3.0.CO;2-O.
[222] Zou C, Zhang Z, Xu X, Gong Q, Li J, Wu C-D. A multifunctional organic–inorganic hy-
brid structure based on MnIII–porphyrin and polyoxometalate as a highly effective
dye scavenger and heterogenous catalyst. J Am Chem Soc 2011;134:87–90.
[223] Matsunaga S, Endo N, Mori W. A new metal carboxylate framework based on por-
phyrin with extended π-conjugation. Eur J Inorg Chem 2011;2011:4550–7.
[224] Gao W-Y, Zhang Z, Cash L, Wojtas L, Chen Y-S, Ma S. Two rare indium-based porous
metal–metalloporphyrin frameworks exhibiting interesting CO 2 uptake.
CrystEngComm 2013;15:9320–3.
[225] Liu T-F, Feng D, Chen Y-P, Zou L, Bosch M, Yuan S, et al. Topology-guided design and
syntheses of highly stable mesoporous porphyrinic zirconium metal–organic
frameworks with high surface area. J Am Chem Soc 2014;137:413–9.
[226] Li K, Huang G, Xu Z, Zhang M, Zeller M, Hunter AD, et al. Multiple bismuth (III)−
thioether secondary interactions integrate metalloporphyrin ligands into func-
tional networks. Inorg Chem 2007;46:4844–9.
[227] Xu L, Wang J, Xu Y, Zhang Z, Lu P, Fang M, et al. A new strategy to construct metal–
organic frameworks with ultrahigh chemical stability. CrystEngComm 2014;16:
8656–9.
[228] Zha Q, Ding C, Rui X, Xie Y. A novel porphyrin-based ligand containing four 4, 4′-
dipyridylamine moieties: syntheses, structures, and luminescent properties of
Mn (II), Cu (II), Zn (II), and Cd (II) coordination polymers. Cryst Growth Des
2013;13:4583–90.
[229] Yang X-L, Xie M-H, Zou C, He Y, Chen B, O’Keeffe M, et al. Porous
metalloporphyrinic frameworks constructed from metal 5, 10, 15, 20-tetrakis (3,
5-biscarboxylphenyl) porphyrin for highly efficient and selective catalytic oxida-
tion of alkylbenzenes. J Am Chem Soc 2012;134:10638–45.
[230] Dybtsev DN, Sapianik AA, Fedin VP. Pre-synthesized secondary building units in the
rational synthesis of porous coordination polymers. Mendeleev Commun 2017;27:
321–31. https://doi.org/10.1016/j.mencom.2017.07.001.
[231] Wang L, Morales J, Wu T, Zhao X, Beyermann WP, Bu X, et al. Assembly of super-
supertetrahedral metal–organic clusters into a hierarchical porous cubic frame-
work. Chem Commun 2012;48:7498–500.
[232] Lal G, Derakhshandeh M, Akhtar F, Spasyuk DM, Bin Lin J, Trifkovic M, et al. Me-
chanical properties of a metal-organic framework formed by covalent cross-
linking of metal-organic polyhedra. J Am Chem Soc 2019;141:1045–53. https://
doi.org/10.1021/jacs.8b11527.
[233] Rhauderwiek T, Wolkersdörfer K, Øien-ØDegaard S, Lillerud KP, Wark M, Stock N.
Crystalline and permanently porous porphyrin-based metal tetraphosphonates.
Chem Commun 2018;54:389–92. https://doi.org/10.1039/c7cc07766a.
[234] Beuerle F, Gole B. Covalent organic frameworks and cage compounds: design and
applications of polymeric and discrete organic scaffolds. Angew Chem Int Ed
2018;57:4850–78. https://doi.org/10.1002/anie.201710190.
[235] Hosono N, Kitagawa S. Modular design of porous soft materials via self-
organization of metal-organic cages. Acc Chem Res 2018;51:2437–46. https://doi.
org/10.1021/acs.accounts.8b00361.
[236] Guillerm V, Weseliński ŁJ, Belmabkhout Y, Cairns AJ, D’elia V, Wojtas Ł, et al. Dis-
covery and introduction of a (3, 18)-connected net as an ideal blueprint for the de-
sign of metal–organic frameworks. Nat Chem 2014;6:673.
[237] Yuan S, Feng L, Wang K, Pang J, Bosch M, Lollar C, et al. Stable metal-organic frame-
works: design, synthesis, and applications. Adv Mater 2018;30:1704303. https://
doi.org/10.1002/adma.201704303.
[238] Mukhopadhyay RD, Kim Y, Koo J, Kim K. Porphyrin boxes. Acc Chem Res 2018;51:
2730–8. https://doi.org/10.1021/acs.accounts.8b00302.
[239] Paille G, Gomez-Mingot M, Roch-Marchal C, Lassalle-Kaiser B, Mialane P, Fontecave
M, et al. A fully noble metal-free photosystem based on cobalt-polyoxometalates
immobilized in a porphyrinic metal-organic framework for water oxidation. J Am
Chem Soc 2018;140:3613–8. https://doi.org/10.1021/jacs.7b11788.
[240] Ohmura T, Usuki A, Fukumori K, Ohta T, Ito M, Tatsumi K. New porphyrin-based
metal− organic framework with high porosity: 2-D infinite 22.2-Å square-grid co-
ordination network. Inorg Chem 2006;45:7988–90.
[241] Wongsakulphasatch S, Nouar F, Rodriguez J, Scott L, Le Guillouzer C, Devic T,
et al. Direct accessibility of mixed-metal (III/II) acid sites through the ratio-
nal synthesis of porous metal carboxylates. Chem Commun 2015;51:
10194–7.
[242] Feng D, Wang K, Wei Z, Chen Y-P, Simon CM, Arvapally RK, et al. Kinetically tuned
dimensional augmentation as a versatile synthetic route towards robust metal–
organic frameworks. Nat Commun 2014;5:5723.
[243] Prochowicz D, Sokołowski K, Justyniak I, Kornowicz A, Fairen-Jimenez D, Friščić T,
et al. A mechanochemical strategy for IRMOF assembly based on pre-designed
oxo-zinc precursors. Chem Commun 2015;51:4032–5.
 S.A. Younis et al. / Advances in Colloid and Interface Science 277 (2020) 102108
[244] Cubillas P, Etherington K, Anderson MW, Attfield MP. Crystal growth of MOF-5
using secondary building units studied by in situ atomic force microscopy.
CrystEngComm 2014;16:9834–41. https://doi.org/10.1039/c4ce01710b.
[245] Majewski MB, Peters AW, Wasielewski MR, Hupp JT, Farha OK. Metal-organic
frameworks as platform materials for solar fuels catalysis. ACS Energy Lett 2018;
3:598–611. https://doi.org/10.1021/acsenergylett.8b00010.
[246] Cui C, Wang Q, Liu Q, Deng X, Liu T, Li D, et al. Porphyrin-based porous organic
framework: An efficient and stable peroxidase-mimicking nanozyme for detection
of H 2 O 2 and evaluation of antioxidant. Sensors Actuators B Chem 2018;277:
86–94. https://doi.org/10.1016/j.snb.2018.08.097.
[247] Hu Z, Zhao D. Metal–organic frameworks with Lewis acidity: synthesis, character-
ization, and catalytic applications. CrystEngComm 2017;19:4066–81. https://doi.
org/10.1039/c6ce02660e.
[248] Wang X, Gao WY, Niu Z, Wojtas L, Perman JA, Chen YS, et al. A metal-
metalloporphyrin framework based on an octatopic porphyrin ligand for chemical
fixation of CO2 with aziridines. Chem Commun 2018;54:1170–3. https://doi.org/
10.1039/c7cc08844b.
[249] Remya VR, Kurian M. Synthesis and catalytic applications of metal–organic frame-
works: a review on recent literature. Int Nano Lett 2019;9:17–29. https://doi.org/
10.1007/s40089-018-0255-1.
[250] Shao P, Yi L, Chen S, Zhou T, Zhang J. Metal-organic frameworks for electrochemical
reduction of carbon dioxide: The role of metal centers. J Energy Chem 2020;40:
156–70. https://doi.org/10.1016/j.jechem.2019.04.013.
[251] Yin D, Liu J, Bo X, Li M, Guo L. Porphyrinic metal-organic framework/macroporous
carbon composites for electrocatalytic applications. Electrochim Acta 2017;247:
41–9. https://doi.org/10.1016/j.electacta.2017.06.176.
[252] Alea-Reyes ME, Penon O, García Calavia P, Marín MJ, Russell DA, Pérez-García L.
Synthesis and in vitro phototoxicity of multifunctional Zn(II)meso-tetrakis(4-
carboxyphenyl)porphyrin-coated gold nanoparticles assembled via axial coordina-
tion with imidazole ligands. J Colloid Interface Sci 2018;521:81–90. https://doi.org/
10.1016/j.jcis.2018.03.014.
[253] Sohrabi S, Dehghanpour S, Ghalkhani M. A cobalt porphyrin-based metal organic
framework/multi-walled carbon nanotube composite electrocatalyst for oxygen
reduction and evolution reactions. J Mater Sci 2018;53:3624–39. https://doi.org/
10.1007/s10853-017-1768-0.
[254] Gao X, DelaCruz S, Zhu C, Cheng S, Gardner D, Xie Y, et al. Surface functionalization
of carbon cloth with cobalt-porphyrin-based metal organic framework for en-
hanced electrochemical sensing. Carbon N Y 2019;148:64–71. https://doi.org/10.
1016/j.carbon.2019.03.040.
[255] Liu M, Wu J, Hou H. Metal–Organic Framework (MOF)-based materials as hetero-
geneous catalysts for C−H bond activation. Chem - A Eur J 2019;25:2935–48.
https://doi.org/10.1002/chem.201804149.
[256] Zou C, Zhang T, Xie MH, Yan L, Kong GQ, Yang XL, et al. Four metalloporphyrinic
frameworks as heterogeneous catalysts for selective oxidation and aldol reaction.
Inorg Chem 2013;52:3620–6. https://doi.org/10.1021/ic3019502.
[257] Aghayan M, Mahmoudi A, Nazari K, Dehghanpour S, Sohrabi S, Sazegar MR, et al. Fe
(III) porphyrin metal–organic framework as an artificial enzyme mimics and its ap-
plication in biosensing of glucose and H2O2. J Porous Mater 2019. https://doi.org/
10.1007/s10934-019-00748-4.
[258] Sun Y, Sun L, Feng D, Zhou H. An in situ one-pot synthetic approach towards mul-
tivariate zirconium MOFs. Angew Chem Int Ed 2016;55:6471–5.
[259] Peh SB, Wang Y, Zhao D. Scalable and sustainable synthesis of advanced porous
materials. ACS Sustain Chem Eng 2019;7:3647–70. https://doi.org/10.1021/
acssuschemeng.8b05463.
[260] Chen YZ, Jiang HL. Porphyrinic metal-organic framework catalyzed heck-reaction:
fluorescence “turn-On” sensing of Cu(II) ion. Chem Mater 2016;28:6698–704.
https://doi.org/10.1021/acs.chemmater.6b03030.
[261] He T, Chen S, Ni B, Gong Y, Wu Z, Song L, et al. Zirconium–porphyrin-based metal–
organic framework hollow nanotubes for immobilization of noble-metal single
atoms. Angew Chem Int Ed 2018;57:3493–8. https://doi.org/10.1002/anie.
201800817.
[262] Liu J, Fan Y-Z, Li X, Wei Z, Xu Y-W, Zhang L, et al. A porous rhodium(III)-porphyrin
metal-organic framework as an efficient and selective photocatalyst for CO2 reduc-
tion. Appl Catal B Environ 2018;231:173–81. https://doi.org/10.1016/j.apcatb.2018.
02.055.
[263] Alhamami M, Doan H, Cheng C. A review on breathing behaviors of metal-organic-
frameworks (MOFs) for gas adsorption. Materials (Basel) 2014;7:3198–250.
https://doi.org/10.3390/ma7043198.
[264] Sharma N, Dhankhar SS, Kumar S, Kumar TJD, Nagaraja CM. Rational design of a 3D
Mn II -metal-organic framework based on a nonmetallated porphyrin linker for se-
lective capture of CO2 and one-pot synthesis of styrene carbonates. Chem - A Eur J
2018;24:16662–9. https://doi.org/10.1002/chem.201803842.
[265] Sharma N, Dhankhar SS, Nagaraja CM. A Mn(II)-porphyrin based metal-organic
framework (MOF) for visible-light-assisted cycloaddition of carbon dioxide with
epoxides. Microporous Mesoporous Mater 2019;280:372–8. https://doi.org/10.
1016/j.micromeso.2019.02.026.
[266] Xiao Y, Guo W, Chen H, Li H, Xu X, Wu P, et al. Ultrathin 2D Cu-porphyrin MOF
nanosheets as a heterogeneous catalyst for styrene oxidation. Mater Chem Front
2019. https://doi.org/10.1039/C9QM00201D.
[267] Xiao P, Xu Y. Recent progress in two-dimensional polymers for energy storage and
conversion: design, synthesis, and applications. J Mater Chem A Mater Energy Sus-
tain 2018;00:1–20. https://doi.org/10.1039/c8ta02820f.
[268] Guo X, Geng S, Zhuo M, Chen Y, Zaworotko MJ, Cheng P, et al. The utility of the tem-
plate effect in metal-organic frameworks. Coord Chem Rev 2019;391:44–68.
https://doi.org/10.1016/j.ccr.2019.04.003.
51
[269] Guan H, Leblanc RJ, Xie S, Yue Y. Recent progress in the syntheses of mesoporous
metal – organic framework materials. Coord Chem Rev 2018;369:76–90. https://
doi.org/10.1016/j.ccr.2018.05.001.
[270] Sanchez-dominguez M, Morales-mendoza G, Rodriguez-vargas MJ, Ibarra-malo CC.
Rodriguez-rodriguez A a, Vela-gonzalez A V, et al. Synthesis of Zn-doped TiO 2
nanoparticles by the novel oil-in-water ( O / W ) microemulsion method and
their use for the photocatalytic degradation of phenol. J Environ Chem Eng 2015;
3:3037–47.
[271] Chu Y, Hou J, Boyer C, Richardson JJ, Liang K, Xu J. Biomimetic synthesis of coordi-
nation network materials: recent advances in MOFs and MPNs. Appl Mater Today
2018;10:93–105. https://doi.org/10.1016/j.apmt.2017.12.009.
[272] Ameloot R, Vermoortele F, Vanhove W, Roeffaers MBJ, Sels BF, De Vos DE. Interfa-
cial synthesis of hollow metal–organic framework capsules demonstrating selec-
tive permeability. Nat Chem 2011;3:382.
[273] Rodenas T, Luz I, Prieto G, Seoane B, Miro H, Corma A, et al. Metal–organic frame-
work nanosheets in polymer composite materials for gas separation. Nat Mater
2015;14:48.
[274] Liu B, Qian D-J, Chen M, Wakayama T, Nakamura C, Miyake J. Metal-mediated co-
ordination polymer nanotubes of 5, 10, 15, 20-tetrapyridylporphine and tris (4-
pyridyl)-1, 3, 5-triazine at the water–chloroform interface. Chem Commun 2006
(30):3175–7.
[275] Sun Y, Zhou HC. Recent progress in the synthesis of metal-organic frameworks. Sci
Technol Adv Mater 2015;16:054202. https://doi.org/10.1088/1468-6996/16/5/
054202.
[276] Vaitsis C, Sourkouni G, Argirusis C. Metal Organic Frameworks (MOFs) and ultra-
sound: a review. Ultrason Sonochem 2019;52:106–19. https://doi.org/10.1016/j.
ultsonch.2018.11.004.
[277] Chen D, Zhao J, Zhang P, Dai S. Mechanochemical synthesis of metal–organic
frameworks. Polyhedron 2019;162:59–64. https://doi.org/10.1016/j.poly.2019.01.
024.
[278] Spoerke ED, Small LJ, Foster ME, Wheeler J, Ullman AM, Stavila V, et al. MOF-
sensitized solar cells enabled by a pillared porphyrin framework. J Phys Chem C
2017;121:4816–24. https://doi.org/10.1021/acs.jpcc.6b11251.
[279] Xiang Z, Cao D, Dai L. Well-defined two dimensional covalent organic polymers: ra-
tional design, controlled syntheses, and potential applications. Polym Chem 2015;
6:1896–911. https://doi.org/10.1039/c4py01383b.
[280] Deria P, Yu J, Balaraman RP, Mashni J, White SN. Topology-dependent emissive
properties of zirconium-based porphyrin MOFs. Chem Commun 2016;52:
13031–4. https://doi.org/10.1039/c6cc07343c.
[281] Ishihara KM, Tian F. Semiconducting Langmuir-Blodgett films of porphyrin paddle-
wheel frameworks for photoelectric conversion. Langmuir 2018;34:15689–99.
https://doi.org/10.1021/acs.langmuir.8b03236.
[282] Park J, Jiang Q, Feng D, Mao L, Zhou HC. Size-controlled synthesis of porphyrinic
metal-organic framework and functionalization for targeted photodynamic ther-
apy. J Am Chem Soc 2016;138:3518–25. https://doi.org/10.1021/jacs.6b00007.
[283] Aziz A, Ruiz-Salvador AR, Hernández NC, Calero S, Hamad S, Grau-Crespo R, et al.
Porphyrin-based metal-organic frameworks for solar fuel synthesis photocatalysis:
band gap tuning: via iron substitutions. J Mater Chem A 2017;5:11894–904.
https://doi.org/10.1039/c7ta01278k.
[284] Guo Z, Yan D, Wang H, Tesfagaber D, Li X, Chen Y, et al. A three-dimensional micro-
porous metal − metalloporphyrin framework. Inorg Chem 2015;54:200–4.
[285] Hou Y, Sun J, Zhang D, Qi D, Jiang J. Porphyrin–alkaline earth MOFs with the highest
adsorption capacity for methyleneblue. Chem - A Eur J 2016;22:6345–52. https://
doi.org/10.1002/chem.201600162.
[286] Cao P, Chen Y, Yin X, Li Z, Cui J, Liu W, et al. Folic acid-nanoscale gadolinium-
porphyrin metal-organic frameworks: fluorescence and magnetic resonance
dual-modality imaging and photodynamic therapy in hepatocellular carcinoma.
Int J Nanomedicine 2018;14:57–74. https://doi.org/10.2147/ijn.s177880.
[287] Kempahanumakkagari S, Kumar V, Samaddar P, Kumar P, Ramakrishnappa T, Kim
KH. Biomolecule-embedded metal-organic frameworks as an innovative sensing
platform. Biotechnol Adv 2018;36:467–81. https://doi.org/10.1016/j.biotechadv.
2018.01.014.
[288] Ling P, Lei J, Ju H. Porphyrinic metal-organic framework as electrochemical probe
for DNA sensing via triple-helix molecular switch. Biosens Bioelectron 2015;71:
373–9. https://doi.org/10.1016/j.bios.2015.04.046.
[289] So MC, Beyzavi MH, Sawhney R, Shekhah O, Eddaoudi M, Al-juaid SS, et al. Post-
assembly transformations of porphyrin-containing metal-organic framework
(MOF) films fabricated via automated layer-by-layer coordination. Chem Commun
2015;51:85–8. https://doi.org/10.1039/c4cc05727a.
[290] Jayachandrababu KC, Sholl DS, Nair S. Structural and mechanistic di ff erences in
mixed-linker zeolitic imidazolate framework synthesis by solvent assisted linker
exchange and de novo routes. J Am Chem Soc 2017;139:5906–15. https://doi.
org/10.1021/jacs.7b01660.
[291] Wu D, Navrotsky A. Thermodynamics of metal-organic frameworks. J Solid State
Chem 2015;223:53–8. https://doi.org/10.1016/j.jssc.2014.06.015.
[292] Jahan M, Bao Q, Loh KP. Electrocatalytically active graphene–porphyrin MOF com-
posite for oxygen reduction reaction. J Am Chem Soc 2012;134:6707–13.
[293] Peng M, Guan G, Deng H, Han B, Tian C, Zhuang J, et al. PCN-224/rGO nanocompos-
ite based photoelectrochemical sensor with intrinsic recognition ability for efficient
p-arsanilic acid detection. Environ Sci Nano 2019;6:207–15. https://doi.org/10.
1039/C8EN00913A.
[294] Wang L, Jin P, Duan S, She H, Huang J, Wang Q. In-situ incorporation of Copper(II)
porphyrin functionalized zirconium MOF and TiO2 for efficient photocatalytic CO2
reduction. Sci Bull 2019;64:926–33. https://doi.org/10.1016/j.scib.2019.05.012.
[295] Zhang Z, Gao WY, Wojtas L, Ma S, Eddaoudi M, Zaworotko MJ. Post-synthetic mod-
ification of porphyrin-encapsulating metal-organic materials by cooperative
52 S.A. Younis et al. / Advances in Colloid and Interface Science 277 (2020) 102108
addition of inorganic salts to enhance CO 2/CH 4 selectivity. Angew Chem Int Ed
2012;51:9330–4. https://doi.org/10.1002/anie.201203594.
[296] Yan Z, Li D, Yin X. Review for chiral-at-metal complexes and metal-organic frame-
work enantiomorphs. Sci Bull 2017;62:1344–54. https://doi.org/10.1016/j.scib.
2017.09.013.
[297] Liu X, Yan Z, Zhang Y, Liu Z, Sun Y, Ren J, et al. Two-dimensional metal-organic
framework/enzyme hybrid nanocatalyst as a benign and self-activated cascade re-
agent for in vivo wound healing. ACS Nano 2019;13:5222–30. https://doi.org/10.
1021/acsnano.8b09501.
[298] Deria P, Mondloch JE, Karagiaridi O, Bury W, Hupp JT, Farha OK. Beyond post-
synthesis modification: evolution of metal-organic frameworks via building block
replacement. Chem Soc Rev 2014;43:5896–912. https://doi.org/10.1039/
c4cs00067f.
[299] Cui P, Wang P, Zhao Y, Sun WY. Fabrication of desired metal-organic frameworks
via postsynthetic exchange and sequential linker installation. Cryst Growth Des
2019;19:1454–70. https://doi.org/10.1021/acs.cgd.8b01628.
[300] Zhang Z, Zhang L, Wojtas L, Nugent P, Eddaoudi M, Zaworotko MJ. Templated syn-
thesis, postsynthetic metal exchange, and properties of a porphyrin-encapsulating
metal-organic material. J Am Chem Soc 2012;134:924–7. https://doi.org/10.1021/
ja209643b.
[301] Zhang Z, Wojtas L, Eddaoudi M, Zaworotko MJ. Stepwise transformation of the mo-
lecular building blocks in a porphyrin-encapsulating metal-organic material. J Am
Chem Soc 2013;135:5982–5. https://doi.org/10.1021/ja4015666.
[302] Li J, Ren Y, Qi C, Jiang H. The first porphyrin-salen based chiral metal-organic frame-
work for asymmetric cyanosilylation of aldehydes. Chem Commun 2017;53:
8223–6. https://doi.org/10.1039/c7cc03499g.
[303] Li J, Fan Y, Ren Y, Liao J, Qi C, Jiang H. Development of isostructural porphyrin-salen
chiral metal-organic frameworks through postsynthetic metalation based on
single-crystal to single-crystal transformation. Inorg Chem 2018;57:1203–12.
https://doi.org/10.1021/acs.inorgchem.7b02631.
[304] Díaz U, Corma A. Ordered covalent organic frameworks, COFs and PAFs. From prep-
aration to application. Coord Chem Rev 2016;311:85–124. https://doi.org/10.1016/
j.ccr.2015.12.010.
[305] Ortiz OL, Ramirez LD. Coordination Polymers and Metal Organic Frameworks:
Properties, Types and Applications (Chemical Engineering Methods and Technol-
ogy). New York: Nova Science Publishers, Inc; 2012.
[306] Jiao L, Seow JYR, Skinner WS, Wang ZU, Jiang H-L. Metal–organic frameworks:
Structures and functional applications. Mater Today 2018. https://doi.org/10.
1016/j.mattod.2018.10.038 xxx.
[307] Cepeda J, Rodríguez-diéguez A. Controlling interpenetration for tuning porosity
and luminescence properties of flexible MOFs based on biphenyl-4,4′-dicarboxylic
acid. CrystEngComm 2016;18:1282–94. https://doi.org/10.1039/C5CE02036K.
[308] Ma W, Yu P, Ohsaka T, Mao L. An efficient electrocatalyst for oxygen reduction re-
action derived from a Co-porphyrin-based covalent organic framework.
Electrochem Commun 2015;52:53–7. https://doi.org/10.1016/j.elecom.2015.01.
021.
[309] Quezada D, Honores J, García M, Armijo F, Isaacs M. Electrocatalytic reduction of
carbon dioxide on a cobalt tetrakis (4-aminophenyl) porphyrin modified electrode
in BMImBF 4. New J Chem 2014;38:3606–12.
[310] Kung CW, Chang TH, Chou LY, Hupp JT, Farha OK, Ho KC. Porphyrin-based metal-
organic framework thin films for electrochemical nitrite detection. Electrochem
Commun 2015;58:51–6. https://doi.org/10.1016/j.elecom.2015.06.003.
[311] Kung CW, Chang TH, Chou LY, Hupp JT, Farha OK, Ho KC. Post metalation of
solvothermally grown electroactive porphyrin metal-organic framework thin
films. Chem Commun 2015;51:2414–7. https://doi.org/10.1039/c4cc09272d.
[312] Ahrenholtz SR, Epley CC, Morris AJ. Solvothermal preparation of an electrocatalytic
metalloporphyrin MOF thin film and its redox hopping charge-transfer mecha-
nism. J Am Chem Soc 2014;136:2464–72.
[313] Solomon MB, Church TL, D’Alessandro DM. Perspectives on metal-organic frame-
works with intrinsic electrocatalytic activity. CrystEngComm 2017;19:4049–65.
https://doi.org/10.1039/c7ce00215g.
[314] Zhu QL, Xu Q. Metal-organic framework composites. Chem Soc Rev 2014;43:
5468–512. https://doi.org/10.1039/c3cs60472a.
[315] Kornienko N, Zhao Y, Kley CS, Zhu C, Kim D, Lin S, et al. Metal–organic frameworks
for electrocatalytic reduction of carbon dioxide. J Am Chem Soc 2015;137:
14129–35.
[316] Zhao Y, Kornienko N, Liu Z, Zhu C, Asahina S, Kuo T-R, et al. Mesoscopic constructs
of ordered and oriented metal–organic frameworks on plasmonic silver
nanocrystals. J Am Chem Soc 2015;137:2199–202.
[317] Hod I, Sampson MD, Deria P, Kubiak CP, Farha OK, Hupp JT. Fe-porphyrin-based
metal–organic framework films as high-surface concentration, heterogeneous cat-
alysts for electrochemical reduction of CO2. ACS Catal 2015;5:6302–9. https://doi.
org/10.1021/acscatal.5b01767.
[318] He J, Zhang Y, He J, Zeng X, Hou X, Long Z. Enhancement of photoredox catalytic
properties of porphyrinic metal–organic frameworks based on titanium incorpora-
tion via post-synthetic modification. Chem Commun 2018;54:8610–3. https://doi.
org/10.1039/C8CC04891F.
[319] Fateeva A, Chater PA, Ireland CP, Tahir AA, Khimyak YZ, Wiper PV, et al. A water-
stable porphyrin-based metal–organic framework active for visible-light
photocatalysis. Angew Chem 2012;124:7558–62.
[320] Liu J, Zhou W, Liu J, Howard I, Kilibarda G, Schlabach S, et al. Photoinduced charge-
carrier generation in epitaxial MOF thin films: high efficiency as a result of an indi-
rect electronic band gap? Angew Chem Int Ed 2015;54:7441–5. https://doi.org/10.
1002/anie.201501862.
[321] Liu J, Zhou W, Liu J, Fujimori Y, Higashino T, Imahori H, et al. A new class of epitaxial
porphyrin metal-organic framework thin films with extremely high photocarrier
generation efficiency: Promising materials for all-solid-state solar cells. J Mater
Chem A 2016;4:12739–47. https://doi.org/10.1039/c6ta04898f.
[322] Chi WS, Roh DK, Lee CS, Kim JH. A shape-and morphology-controlled metal organic
framework template for high-efficiency solid-state dye-sensitized solar cells. J
Mater Chem A 2015;3:21599–608.
[323] Xu G, Yamada T, Otsubo K, Sakaida S, Kitagawa H. Facile “modular assembly” for
fast construction of a highly oriented crystalline MOF nanofilm. J Am Chem Soc
2012;134:16524–7.
[324] Lopez HA, Dhakshinamoorthy A, Ferrer B, Atienzar P, Alvaro M, Garcia H. Photo-
chemical response of commercial MOFs: Al2 (BDC) 3 and its use as active material
in photovoltaic devices. J Phys Chem C 2011;115:22200–6.
[325] Usov PM, Ahrenholtz SR, Maza WA, Stratakes B, Epley CC, Kessinger MC, et al. Co-
operative electrochemical water oxidation by Zr nodes and Ni-porphyrin linkers of
a PCN-224 MOF thin film. J Mater Chem A 2016;4:16818–23. https://doi.org/10.
1039/c6ta05877a.
[326] Alkordi MH, Liu Y, Larsen RW, Eubank JF, Eddaoudi M. Zeolite-like metal-
organic frameworks as platforms for applications: On metalloporphyrin-
based catalysts. J Am Chem Soc 2008;130:12639–41. https://doi.org/10.
1021/ja804703w.
[327] Larsen RW, Wojtas L, Perman J, Musselman RL, Zaworotko MJ, Vetromile CM. Mim-
icking heme enzymes in the solid state: metal–organic materials with selectively
encapsulated heme. J Am Chem Soc 2011;133:10356–9.
[328] Kockrick E, Lescouet T, Kudrik EV, Sorokin AB, Farrusseng D. Synergistic effects of
encapsulated phthalocyanine complexes in MIL-101 for the selective aerobic oxi-
dation of tetralin. Chem Commun 2011;47:1562–4. https://doi.org/10.1039/
c0cc04431h.
[329] Zalomaeva OV, Kovalenko KA, Chesalov YA, Mel’Gunov MS, Zaikovskii VI, Kaichev
VV, et al. Iron tetrasulfophthalocyanine immobilized on metal organic framework
MIL-101: Synthesis, characterization and catalytic properties. Dalton Trans 2011;
40:1441–4. https://doi.org/10.1039/c0dt01474e.
[330] Beyzavi MH, Vermeulen NA, Howarth AJ, Tussupbayev S, League AB, Schweitzer
NM, et al. A hafnium-based metal–organic framework as a nature-inspired tandem
reaction catalyst. J Am Chem Soc 2015;137:13624–31.
[331] Wang H, Ding H, Meng X, Wang C. Two-dimensional porphyrin- and
phthalocyanine-based covalent organic frameworks. Chin Chem Lett 2016;27:
1376–82. https://doi.org/10.1016/j.cclet.2016.05.020.
[332] Liang J, Xie YQ, Wu Q, Wang XY, Liu TT, Li HF, et al. Zinc porphyrin/imidazolium in-
tegrated multivariate zirconium metal-organic frameworks for transformation of
CO 2 into cyclic carbonates. Inorg Chem 2018;57:2584–93. https://doi.org/10.
1021/acs.inorgchem.7b02983.
[333] Tong M, Dong S, Wang K, Suo G. A porphyrin MOF and ionic liquid biocompatible
matrix for the direct electrochemistry and electrocatalysis of cytochrome c. J
Electrochem Soc 2017;164:B200–4. https://doi.org/10.1149/2.0911706jes.
[334] Morris W, Volosskiy B, Demir S, Gándara F, McGrier PL, Furukawa H, et al. Synthe-
sis, structure, and metalation of two new highly porous zirconium metal–organic
frameworks. Inorg Chem 2012;51:6443–5.
[335] Usov PM, Huffman B, Epley CC, Kessinger MC, Zhu J, Maza WA, et al. Study of elec-
trocatalytic properties of metal-organic framework PCN-223 for the oxygen reduc-
tion reaction. ACS Appl Mater Interfaces 2017;9:33539–43. https://doi.org/10.
1021/acsami.7b01547.
[336] Cui H, Wang Y, Wang Y, Fan YZ, Zhang L, Su CY. A stable and porous iridium(III)-
porphyrin metal-organic framework: Synthesis, structure and catalysis.
CrystEngComm 2016;18:2203–9. https://doi.org/10.1039/c6ce00358c.
[337] Wang Y, Cui H, Wei ZW, Wang HP, Zhang L, Su CY. Engineering catalytic coordina-
tion space in a chemically stable Ir-porphyrin MOF with a confinement effect
inverting conventional Si-H insertion chemoselectivity. Chem Sci 2016;8:775–80.
https://doi.org/10.1039/C6SC03288E.
[338] Makiura R, Motoyama S, Umemura Y, Yamanaka H, Sakata O, Kitagawa H. Surface
nano-architecture of a metal–organic framework. Nat Mater 2010;9:565–71.
[339] Zhou G, Wang YS, Jin Z, Zhao P, Zhang H, Wen Y, et al. Porphyrin–palladium hy-
dride MOF nanoparticles for tumor-targeting photoacoustic imaging-guided
hydrogenothermal cancer therapy. Nanoscale Horizons 2019. https://doi.org/10.
1039/C9NH00021F.
[340] Dutta G, Jana AK, Natarajan S. Assembling porphyrins into extended network struc-
tures by employing aromatic dicarboxylates: synthesis, metal exchange, and het-
erogeneous catalytic studies. Chem - A Eur J 2017;23:8932–40. https://doi.org/10.
1002/chem.201700985.
[341] Castro KADF, Figueira F, Mendes RF, Cavaleiro JAS, Neves M da GPMS, Simões MMQ,
et al. Copper–porphyrin–metal–organic frameworks as oxidative heterogeneous
catalysts. ChemCatChem 2017;9:2939–45. https://doi.org/10.1002/cctc.
201700484.
[342] Xie M-H, Yang X-L, Wang Wu C-D. Chem Commun 2011;47:5521–3.
[343] Lee DH, Kim S, Hyun MY, Hong J-Y, Huh S, Kim C, et al. Controlled growth of nar-
rowly dispersed nanosize hexagonal MOF rods from Mn (III)–porphyrin and In
(NO 3) 3 and their application in olefin oxidation. Chem Commun 2012;48:
5512–4.
[344] Xu W, Zhang Z, Zhao X, Li J. Catalytically active metal organic framework based on a
porphyrin modified by electron-withdrawing groups. J Coord Chem 2017;70:
746–55. https://doi.org/10.1080/00958972.2016.1267728.
[345] Anderson HL. Building molecular wires from the colours of life: conjugated porphy-
rin oligomers. Chem Commun 1999(23):2323–30.
[346] Goldberg I. Metalloporphyrin molecular sieves. Chem Eur J 2000;6:3863–70.
[347] Burrell AK, Officer DL, Plieger PG, Reid DCW. Synthetic routes to multiporphyrin ar-
rays. Chem Rev 2001;101:2751–96.
[348] Kim D, Osuka A. Directly linked porphyrin arrays with tunable excitonic interac-
tions. Acc Chem Res 2004;37:735–45.
 S.A. Younis et al. / Advances in Colloid and Interface Science 277 (2020) 102108
[349] Tashiro K, Aida T. Metalloporphyrin hosts for supramolecular chemistry of fuller-
enes. Chem Soc Rev 2007;36:189–97.
[350] Li W-S, Aida T. Dendrimer porphyrins and phthalocyanines. Chem Rev 2009;109:
6047–76.
[351] Kadish KM, Smith KM, Guilard R. Handbook of Porphyrin Science with Applications
to Chemistry, Physics, Materials Science, Engineering, Biology and Medicine. , vol.
6–10Singapore: World Scientific Publishing Co. Pte. Ltd; 2010.
[352] Musselman RL, Larsen RW, Hoffman BM. Electronic spectra of porphyrins in the
solid state: Newly observed transitions, collective and structural effects, and
protein-mimicking environments. Coord Chem Rev 2013;257:369–80. https://
doi.org/10.1016/j.ccr.2012.08.015.
[353] Fuhrhop J-H. Porphyrin assemblies and their scaffolds. Langmuir 2013;30:1–12.
[354] Gottfried JM. Surface chemistry of porphyrins and phthalocyanines. Surf Sci Rep
2015;70:259–379. https://doi.org/10.1016/j.surfrep.2015.04.001.
[355] Sandland J, Malatesti N, Boyle R. Porphyrins and related macrocycles: combining
photosensitization with radio- or optical-imaging for next generation theranostic
agents. Photodiagn Photodyn Ther 2018;23:281–94. https://doi.org/10.1016/j.
pdpdt.2018.06.023.
[356] Aguilar-Ortíz E, Jalilian AR, Ávila-Rodríguez MA. Porphyrins as ligands for 64 cop-
per: background and trends. Medchemcomm 2018;9:1577–88. https://doi.org/10.
1039/C8MD00263K.
[357] Ding Y, Chen YP, Zhang X, Chen L, Dong Z, Jiang HL, et al. Controlled intercalation
and chemical exfoliation of layered metal-organic frameworks using a chemically
labile intercalating agent. J Am Chem Soc 2017;139:9136–9. https://doi.org/10.
1021/jacs.7b04829.
[358] Cao F, Zhao M, Yu Y, Chen B, Huang Y, Yang J, et al. Synthesis of two-dimensional
CoS1.097/nitrogen-doped carbon nanocomposites using metal-organic framework
nanosheets as precursors for supercapacitor application. J Am Chem Soc 2016;138:
6924–7. https://doi.org/10.1021/jacs.6b02540.
[359] Zhao Y, Dong Y, Lu F, Ju C, Liu L, Zhang J, et al. Coordinative integration of a metal-
porphyrinic framework and TiO 2 nanoparticles for the formation of composite
53
photocatalysts with enhanced visible-light-driven photocatalytic activities. J
Mater Chem A 2017;5:15380–9. https://doi.org/10.1039/c7ta03840b.
[360] Sadeghi N, Sharifnia S, Do TO. Enhanced CO2 photoreduction by a graphene-
porphyrin metal-organic framework under visible light irradiation. J Mater Chem
A 2018;6:18031–5. https://doi.org/10.1039/c8ta07158f.
[361] Kung C, Li Y, Lee M, Wang S, Chiang W-H, Ho K-C. In situ growth of porphyrinic
metal – organic framework nanocrystals on graphene nanoribbons for the electro-
catalytic oxidation of nitrite. J Mater Chem A 2016;4:10673–82. https://doi.org/10.
1039/c6ta02563c.
[362] Jia H, Sun Z, Jiang D, Du P. Covalent cobalt porphyrin framework on multiwalled
carbon nanotubes for efficient water oxidation at low overpotential. Chem Mater
2015;27:4586–93.
[363] Masih D, Chernikova V, Shekhah O, Eddaoudi M, Mohammed OF. Zeolite-like
metal-organic framework (MOF) encaged Pt(II)-porphyrin for anion-selective
sensing. ACS Appl Mater Interfaces 2018;10:11399–405. https://doi.org/10.1021/
acsami.7b19282.
[364] Baroni N, Turshatov A, Oldenburg M, Busko D, Adams M, Haldar R, et al. Materials
chemistry frontiers facile loading of thin-film surface-anchored. Mater Chem Front
2017;1:1888–94. https://doi.org/10.1039/c7qm00142h.
[365] Li C, Qiu W, Long W, Deng F, Bai G, Zhang G, et al. Synthesis of porphyrin@MOFs
type catalysts through “one-pot” self-assembly. J Mol Catal A Chem 2014;393:
166–70. https://doi.org/10.1016/j.molcata.2014.05.023.
[366] Ding S-Y, Wang W. Covalent organic frameworks (COFs): from design to applica-
tions. Chem Soc Rev 2013;42:548–68. https://doi.org/10.1039/C2CS35072F.
[367] Zhang YB, Su J, Furukawa H, Yun Y, Gándara F, Duong A, et al. Single-crystal struc-
ture of a covalent organic framework. J Am Chem Soc 2013;135:16336–9. https://
doi.org/10.1021/ja409033p.
[368] Liu J, Lukose B, Shekhah O, Arslan HK, Weidler P, Gliemann H, et al. A novel series of
isoreticular metal organic frameworks: Realizing metastable structures by liquid
phase epitaxy. Sci Rep 2012;2:1–5. https://doi.org/10.1038/srep00921.