10.1002/ange.

202101644
Figure 1 Reticular chemistry design concepts.
 ! Sci. Adv. 2018; 4 : eaat9180
Fig. 2. The reticular table.
Figure 2. Top: a few carboxylate-based MOFs, reflecting chemical, structural and topological
diversity. Bottom: Timeline showing some major MOFs achievements, along with the yearly
number of MOFs publications and reported MOFs structures to the CSD.
 Mesoporous,
stable, Zn2+ MOF
DUT-60
Figure 3 Illustrative timeline of the milestones in the multicomponent and
multivariate MOFs.
Science 2013, Vol. 341, pp. 882-885
Complexity in MOFs through the multi-SBU approach. (A) Crystal structure of
[M3OL3]2(TCPP-M)3 with an underlying stp topology. The well-mixed scenario
(mixed-metal SBUs; left) is observed for metals with similar radii and
electronegativity (for example, Fe2+ and Ni2+). In contrast, for metals with
significantly different radii and electronegativity (for example, Mn2+ and Fe2+), the
domain scenario (right) is observed.
Figure 4. Illustrative timeline of the milestones in the COFs synthesis.
Figure 5. Illustrative timeline of the milestones in the ZIFs synthesis.
Figure 6. Illustrative timeline of the milestones in the characterization
of reticular materials.
Figure 7. Illustrative timeline of the milestones in the computational
modeling of reticular frameworks.
The modeling and simulation of reticular frameworks, specifically, the
building of mathematical models that replicate the framework
structures, of which the physicochemical properties, interactions, and
dynamics are studied with algorithms derived from known physical
principles and chemical knowledge. The aims, as such, include (i) the
accurate representation of the structures, (ii) the precise calculation
of their energy and thus physicochemical properties, (iii) the proper
simulation of the interactions within frameworks and with guests, (iv)
the achievement of affordable computational tools, and (v) their
generalized establishment to enable predictive studies of new
materials.

https://www.kurzweilai.net/a-world-record-for
-highest-surface-area-material
Figure 8. Illustrative timeline of the milestones in the postsynthetic
modification.
Synthesis of MOF−Polymer hybrid materials. First, a PSM step in which the −NCS
groups on the MOF (red semicircles) undergo covalent PSM with an excess of
amine-functionalized polymer (blue). Subsequently, through the introduction of a
diisothiocyanate molecule (red), chains of polymer are grown resulting in a
monolithic MOF−PTU (polythiourea) hybrid material.

This material was spray coated onto Nyco (nylon and cotton blended textile) fibers.
The covalently linked spray coating showed excellent adhesion to the Nyco fibers,
whereas a noncovalent control spray coating (unfunctionalized UiO-66) exhibits
clear phase separation between the MOF and polymer component.
Scheme for the design of DNA-functionalized MOFs through coordinative PSM.
Single-stranded DNA with phosphate coordinating groups was tethered to the MOF
via the SBUs. Subsequently, with the addition of AuNPs surface coated with a
complementary DNA strand, MOF particles are assembled around the AuNP as a
function of the double helix formation.
In other words, gold nanoparticles (AuNPs) were surface coated with a
complementary DNA sequence to that on the surface of the MOF, which enabled
self-assembly as a function of the oligonucleotide sequences
 ! Adv. Funct. Mater. 2020, 2000238

The polymeric phosphate units dangling from the bacterial cell wall coordinate to
the unsaturated metal sites of Zr clusters on a MOF monolayer.

! When the anaerobic bacteria Morella thermoacetica is uniformly wrapped with a MOF
monolayer of nanometer thickness, their inherent susceptibility to O2 and reactive oxygen
species was overcome. The cytoprotection is endowed by the MOF-catalyzed decomposition
of reactive oxygen species accumulated on the cell surface, with an activity 600 times higher
than that of zirconia nanoparticles, thus reducing the death of the strictly anaerobic bacteria
by fivefold in air. The artificially enhanced tolerance to O2 enabled the MOF-wrapped
bacteria to continuously produce acetate from CO2 fixation under oxidative stress.
Figure 9. Illustrative timeline of the milestones in the MOF
nanoparticles.
LaMer Model to Account for the Structural Evolution of MOF Crystals through
Nucleation and Growth
 Surface modification by coordination modulation: ligantes
monodentados (ácido acético, ácido fórmico, ácido
benzoico, piridina, ...) que influenciam no processo de
reticulação Adv. Mater. 2018, 1704303

Schematic illustration of coordination modulation, where a monodentate ligand,

or modulator, caps MOF crystal growth, using MOF-5 as an idealized example.
Chem. Commun., 2015, 51, 5199
CrystEngComm 2016, 18, 4359
 Defects induced by missing linkers

(a) Section of the crystal structure of NOTT-101(copper cations linked by 1,1:4,1-

terphenyl-3,3-5,5-tetracarboxylate units); (b) Simplified diagram to illustrate the
introduction of defects within NOTT-101 (rather than surface termination) when
isophthalate modulators are incorporated into the synthesis of the MOF, generating
mesopores with additional functional groups (labelled R)
The effect on crystal shape of varying the ratios of face-selective
carboxylic acid and amine modulators during the synthesis of the
pillared MOF [Cu2(ndc)2(dabco)]n.
Post-synthetic surface modification

Exchange of surface ligands from (a) 1,4-benzenedicarboxylate units to (b)

fluorescent BODIPY linkers in [Zn2(1,4-bdc)2(dabco)]n. Ligand exchange only occurs
at the carboxylate terminated [100] surfaces of the MOF as a result of the
functional group complementarity with the BODIPY ligand.
Exchange of surface ligands of ZIF-8 allows attachment of (a) fluorescent BODIPY
dyes to (b) visualise the surface ligand exchange by fluorescence microscopy, while
incorporation of (c) hydrophobic surface functionality such as 5,6-
dimethylbenzimidazole significantly increases the hydrolytic stability of ZIF-8.
(a) Synthesis of UiO-66-N3. (b)
Schematic surface attachment of
oligonucleotides to UiO-66-N3
nanoparticles. (c) Chemical
structure of the strain-promoted
click reaction between 2-N3-1,4-
bdc ligands of the MOF and
DBCO functionalised DNA.
Aplicação: DNA-Functionalized MOF Nanoparticles for
Intracellular Delivery of Proteins

JACS, 2019
 Modo alternativo de evitar a aglomeração dos núcleos: to introduce a confined
reaction environment into the synthesis: it can be a microdroplets in a spray-
drying method, for instance, or using surfactants (in this case, the morphology
can be controlled by the shape of microemulsions)

A spray-drying continuous-flow method for

simultaneous synthesis and shaping of
microspherical high nuclearity MOF beads
Synthesis and self-assembly of Fe-soc-
MOF nanocubes directed by emulsion
Figure 10. Illustrative timeline of the milestones in the reticular thin
films.
Schematic diagram for the step-by-step approach for the growth of the MOFs on
substrates functionalized with SAMs (Self-Assembled Monolayers): Au substrate
immersed into solution of organo(carboxylate)thiols
 Films of Ni3(HITP)2 (HITP = 2,3,6,7,10,11-
hexaiminotriphenylenesemiquinonate)
deposited on quartz substrates
(conductivity = 40 S·cm−1)

J. Am. Chem. Soc. 2014, 3, 2

Figure 11. Illustrative timeline of the milestones in the shaping reticular
materials at the meso and bulk scale.
(a) A binary system composed of green [Cu2(1,4-ndc)2(dabco)]n on colourless [Zn2(1,4-
ndc)2(dabco)]n. (b) A core-shell-shell triple layer system of IRMOF-3@MOF-5@IRMOF-3. (c) A so
called Janus hybrid, where the coverage of MOF-5 (also known as IRMOF-1) by IRMOF-3 is
limited by adhesion of the base of the core crystal to a surface. (d) Schematic showing face-
selective epitaxial growth in a pillared MOF. (e) Face-selective epitaxial growth of orange
[Zn2(1,4-ndc)2(dpndi)]n on the [001] faces only of colourless [Zn2(1,4-ndc)2(dabco)]n.
The ‘‘sandwich’’ structure allowed for the catalytic performance of the composite to
be tuned away from the highly favorable hydrogenation of the carbon–carbon
bonds, to the much less favorably selective hydrogenation of the carbon–oxygen
bonds. With this new catalytic pathway easily accessible, MIL-101@Pt@MIL-101 was
successfully tested as a catalyst for the selective reduction of α,β-unsaturated
aldehydes to unsaturated alcohols
a) Photograph of the self-assembled superstructures resulting from the
centrifugation of an aqueous colloidal solution of ZIF-8 particles of different sizes.
Note here the opalescence visible to the naked eye, which confirms a certain degree
of ordering in these structures. b) Representative FE-SEM image of self-assembled
superstructures resulting from this centrifugation step.
Scale bars: 1 μm (b, left) and 5 μm (b, right). Nat. Chem. 2018, 10, 78–84
(Left) Representative FE-SEM image of a crosssection of the self-assembled
superstructure, showing the rhombohedral lattice. (right) Densest packing obtained
from Floppy-Box Monte Carlo simulations, confirming the same type of
rhombohedral lattice obtained experimentally. Bottom right: unit cell of the
rhombohedral lattice
In situ nanocasting synthesis of SOM-ZIF-8 and its structure
confirmation. (A) Schematic diagram of the strategy to design SOM-
ZIF-8.THF (SOM = single-crystal ordered macropore)

Monodisperse polystyrene spheres (PSs) were assembled into highly ordered 3D

PS monoliths. ZIF-8 precursors were then filled into the PS monolith interstices to
form “precursor@PS” monoliths, which were subsequently soaked in
CH3OH/NH3·H2O mixed solutions. With the adjusted balance then between
nucleation versus growth, the precursors smoothly turned into oriented and 3D-
ordered ZIF-8 single crystals
Science 2018, 359, 206–210.
(B) Representative SEM image of SOM-ZIF-8 (3,0.5) that displays a
tetrakaidecahedron morphology. (C) SEM images of individual
crystals taken from four different directions. The ordered
arrangement of macropores on the surface of six square planes and
eight triangle planes inherited {100} and {111} planes of the colloidal
PS template, respectively.
(D) SEM image of the ZIF-8 grown on the external surface of the PS
template. (E and F) SEM images of two selected semifinished SOM-
ZIF-8(3, 0.5) crystals, confirming their oriented growth within
ordered voids. Yellow areas, {100} planes of macropore
arrangements; red areas, {111} planes of macropore arrangements.
(G) Illustration of the shaping and templating effects of the 3D-
ordered PS template on the morphologic evolution of SOM-ZIF-8.
Schematic illustration of direct patterning of MOF films by XRL and EBL. The MOF film is
irradiated by X-rays through a mask (XRL) or by direct electron-beam writing (EBL). The pattern
is developed by removing the irradiated part in DMSO. Nat. Mater. 2021, 20, 93–99
e, Schematic illustration of the direct patterning of MOF single crystals
by XRL. f,g, SEM images of ~100 μm ZIF-8-dc-im single crystals after
XRL patterning with a negative (f) and positive (g) hexagonal grid mask.
The resulting particles retain their single-crystalline nature. Scale bars:
f, 20 μm; g, 200 μm and 50 μm for inset.
Figure 12. Illustrative timeline of the milestones in the monolithic
reticular materials.
Photograph of an aerogel obtained from 0.2 M trimesic acid solution in
comparison with an air-dried xerogel of similar original size (a) and scanning
electron micrographs (SEM) of a xerogel (b) and an aerogel sample (c).
Nature Materials 17, 174–179, 2018

powdHKUST-1
Simple aggregation of primary
particles of ~ 50 nm
monoHKUST-1
continuous phase where the primary
particles can no longer be observed,
surface is more compact with minimal
amount of interstitial space
Nanoindentation on monoHKUST-1. a,b, Young’s modulus and hardness, respectively, as a
function of indentation depth. Averaged properties were derived from 60 indents, using
penetration depths of 200–2,000 nm, thus ensuring results are free from surface defects and tip
calibration artefacts. The inset in a shows the load–displacement raw data. The inset in b shows
the hardness of monoHKUST-1 is double that of its conventional polycrystalline counterpart. c,
Optical micrograph showing the array of residual indents, showing no evidence of radial
cracking. d, AFM profile depicting the 3D topography of a representative indent, showing there
is no sign of surface cracking, and thus indicating good mechanical resilience of the monolith.
 UiO-66 washed in ethanol and dried at 200 °C (monoUiO-66_A). e UiO-66 washed
in ethanol and dried at 30 °C (monoUiO-66_B). f UiO-66 washed in DMF and dried
at 30 °C (monoUiO-66_C). g UiO-66 washed in DMF with extended centrifugation
and then dried at 30 °C (monoUiO-66_D).

Synthesis of UiO-66 gel. Benzene-1,4-dicarboxylic acid (1.20 g, 7.25 mmol) and zirconium(IV)
oxychloride octahydrate (1.61 g, 5.0 mmol) were dissolved in DMF (30 ml, 99 %). Concentrated
HCl (1.5 ml, 37 %) and glacial acetic acid (2.0 ml) were added with vigorous stirring. The resulting
solution was sealed in a 100 ml Pyrex Schott bottle and heated to 100 °C for 2 h.

Synthesis of UiO-66_A-D. N,N-dimethylformamide (50ml) was added to the UiO-66 gel as

synthesised above and vigorously mixed. The diluted UiO-66 suspension (7.5ml per tube) was
centrifuged (3min, 5500 rpm) and the supernatant decanted. The gel was washed, centrifuged
(5500 rpm) and dried to produce a range of monoliths. The obtained monolith was soaked in
acetone (3 × 5ml, 24 h) and methanol (3 × 5ml, 24 h) and then dried at room temperature
overnight. It was then activated by heating to 110 °C under vacuum for 8 h.
Gas adsorption isotherms and particle densification. a–c Variations in gas
adsorption isotherms and corresponding changes in working capacity for Type I, II
and V isotherms, respectively. d Representation of the abundant interstitial space
amongst non-densified MOF particles (compared with a densified monolith) what
reduce the adsorbent volumetric capacity.
Type II and IV adsorbents that
micropores rapidly
isotherms do maximise working
saturate at low P capacity via Type V
pressure with only not plateau at high
S-shaped isotherms,
marginal gains P, but still show a
e.g., some flexible
achieved by relatively high MOFs with unusual
applying higher P uptake at low P adsorption behaviour
The density distribution and a snapshot of simulated N2 adsorption (navy blue
spheres) at 0.7 P/Po (i.e., before capillary condensation — the micropores and the
mesopore walls are completely filled by N2, whereas the centre of the mesopore
remains empty) between two UiO-66 crystals separated by a 2.3 nm mesopore.
 The density distribution and a snapshot of CH4 (grey spheres) uptake into UiO-66
crystals separated by a 2.3 nm mesopore (comparable with monoUiO-66_D) at 80
bar.

Therefore, GCMC simulations demonstrated that the physical origin of this enhanced
uptake capacity lies in substantial gas condensation in the mesopores at high
pressure