Small - 2021 - Ma - Luminescent Covalent Organic Frameworks For Biosensing and Bioimaging Applications

Review
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Luminescent Covalent Organic Frameworks for Biosensing

and Bioimaging Applications
Jianxin Ma, Tong Shu,* Yanping Sun, Xiang Zhou, Chenyu Ren, Lei Su, and Xueji Zhang*
and have attracted wide attention because

Luminescent covalent organic frameworks (LCOFs) have attracted significant of their Lego®-like structures and exotic
attention due to their tunability of structures and photophysical properties photo physical and luminescent proper-
at molecular level. LCOFs are built to highly ordered and periodic 2D or 3D ties.[1–5] They are emissive crystalline
framework structures through covalently assembling with various lumino- porous polymers, enabling the integra-
tion of various molecular luminophore
phore building blocks. Recently, the advantages of LCOFs including prede-
building blocks into highly ordered and
signed properties of structure, unique photoluminescence, hypotoxicity and periodic 2D or 3D framework struc-
good biocompatibility and tumor penetration, broaden their applications tures.[6–9] The moldability and maneuver-
in biorelated fields, such as biosensing, bioimaging, and drug delivery. A ability of structures contribute to their
specific review that analyses the advances of LCOFs in the field of biosensing unique advantages including precise con-
trol over both skeletons and pores[10,11]
and bioimaging is thus urged to emerge. Here the construction of LCOFs is
and predesigned functional moieties inte-
reviewed first. The synthetic chemistry of LCOFs highlights the key role of grated at the atomic level precisely,[12] high
chemical linkages, which not only concrete the building blocks but also affect surface area,[11,13] relatively large pore aper-
the optical properties and even can act as the responsive sites for potential tures,[13–17] low density,[10] high thermal
sensing applications. How to brighten LCOFs are clarified through description stability,[10,14,18] and fine-tuned chemical
of structure managements. The ability to utilize the luminescence of LCOFs and physical properties. LCOFs thus have
found a variety of their applications in
for applications in biosensing and bioimaging is discussed using state-of-the-
gas storage and adsorption, molecular
art examples of varied practical goals. A prospect finally addresses opportuni- separation,[19–21] catalysis,[22] and optoelec-
ties and challenges the development of LCOFs facing from chemistry, physics tronics.[23–25] Recently, the development of
to the applications, according to their current progress. LCOFs with photoluminescent tunability
has spurred an increasing application
in chemical sensing, such as quantita-
1. Introduction tive detection of environmental hazards, including nitroexplo-
sives,[26–31] and aromatic small molecule compounds.[21,32]
Luminescent covalent organic frameworks (LCOFs) are an The photophysical properties of LCOFs and their chemical
emerging new class of covalent organic frameworks (COFs) sensing applications have been well reviewed by Haug et al.[1]
and Xue et al.,[4] respectively, demonstrating their potential
J. Ma, T. Shu, Y. Sun, X. Zhou, L. Su, X. Zhang abilities as luminescent probes. Very recently, the desirable
Research Center for Biosensor and Nanotheranostic biocompatibility of COFs has aroused a booming interest in
School of Biomedical Engineering their potential biomedical applications.[33–35] As emissive COFs,
Health Science Center the applications of LCOFs have also been expanded to biolog-
Shenzhen University
Guangdong 518060, P. R. China
ical fields, such as disease diagnosis[36] and drug delivery.[37]
E-mail: shutong@szu.edu.cn; zhangxueji@szu.edu.cn LCOFs as intriguing bioprobes have their unique advantages,
J. Ma, Y. Sun, C. Ren including high in vivo stability and loading capacities, good
Beijing Key Laboratory for Bioengineering and Sensing Technology biocompatibility, and desirable degradability.[38,39] However, the
Research Center for Bioengineering and Sensing Technology applications of LCOFs in biosensing and bioimaging have been
School of Chemistry and Biological Engineering rarely summarized by far. Here, we investigate the reports of
University of Science and Technology Beijing
Beijing 100083, P. R. China LCOFs and dedicate to fundamentally understanding the devel-
T. Shu opment of LCOFs in the fields of biosensing and bioimaging.
Guangdong Provincial Key Laboratory of Luminescence In this review, the synthetic chemistry of LCOFs has been
from Molecular Aggregates understood and summarized through classification of linkages.
South China University of Technology Meanwhile, the common luminescent building blocks and
Guangzhou 510640, China
synthetic methods of LCOFs are described. Then, the strategies
The ORCID identification number(s) for the author(s) of this article of brightening LCOFs have been classified into two parts: selec-
can be found under https://doi.org/10.1002/smll.202103516. tion of building blocks and administration of intra/intermolec-
ular interactions. The photophysical properties of LCOFs have
DOI: 10.1002/smll.202103516 been applied to the fields of biosensing and bioimaging, which
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include fluorescent sensing of molecular analytes, cell imaging, yellow luminescence upon UV radiation.[48] Additionally, the
in vivo imaging, and other biorelated functions. Lastly, an out- phosphorescent COFs (e.g., Dio⊂BZL-COF) could be synthe-
look addresses the current advances and existing challenges sized via condensation of HHTP and 4,4′-benzildiboronic acid
facing the issues from chemistry, physics and materials to the (BZLBA) in a dioxane/mesitylene mixture at 100 °C for 72 h.
scope of their applications. BZLBA was a representative crystallization-induced phospho-
rescence organic phosphor and the resultant deep-green COF
powders displayed intense yellow phosphorescence centered at
2. Synthetic Chemistry of LCOFs 545 nm upon UV irradiation at cryogenic temperature such as
77 K.[49]
LCOFs can stably emit fluorescence or phosphorescence under The boroxine-linked LCOFs are synthesized through dehy-
the irradiation of excitation light with certain wavelength. They dration of boronic acids. After the reaction, three boronic acid
usually contain large π-conjugated building blocks or have a molecules are converged and form a cyclic six-membered
large π-conjugated system as well as inherent rigid structures.[4] boroxine with a planar structure, as fully shown in Scheme 2.[47]
LCOFs have been thus synthesized mainly through the aromatic Wan et al. reported the synthesis of a cubic shaped PPy-COF
building blocks such as triphenylene,[6,40] pyrene,[7,25,32,41–44] by self-condensation of PDBA. The PPy-COF was pale-yellow
triazine,[30,45] and porphyrin [29,46] via the dehydration of boronic solid and was highly blue-luminescent with an emission peak
acids, the condensation of boronic esters and the Schiff base at 484 nm upon excitation at 414 nm. It was also the first
reaction of aldehydes and hydrazine (H2NNH2) or amines. example of photoconductive COFs and thus was able to be
According to different linking methods, the combos of lumi- used in optoelectronics and photovoltaics.[25] Subsequently,
nescent monomers can be explicitly outlined by a series of a series of boroxine-linked COFs such as Ph-COF, BPh-COF,
orthogonal charts. Interestingly, after classification and divi- and diphenylbutadiynebisboronic acid-COF have been prepared
sion, it can be found that there are considerable blanks in the via self-condensation of several polyfunctional boronic acids.
cross charts of varied monomers, which provide possibilities Highly emissive COF colloids could be attained upon exist-
and opportunities for the synthesis of novel LCOFs. These ence of stabilizing cosolvent acetonitrile (Figure 2A) and such a
blanks are expected to be filled in the near future. considerable emission enhancement was attributed to through-
space communication of chromophores between COF sheets
(Figure 2B).[50]
2.1. Chemical Linkages of LCOFs
2.1.1. Boronic Esters and Boroxines 2.1.2. Imines
The boron-containing LCOFs can be generally divided into two Imine bonds with significantly higher stability than the boronic
types: boronic esters and boroxine rings. The boronic ester- esters are formed by condensation of aldehydes and amines
linked COFs are synthesized via condensation of boronic acids in the presence of organic acid or Lewis acid catalyst.[5,47] As
and catechol derivatives. The reactions generate five-membered shown in Scheme 3, a full list of the imine-linked LCOFs is
BO2C2 rings, facilitating the formation of COFs with an entirely given. The imine-linked LCOFs are emissive and present pla-
coplanar extended sheet structure.[47] A full list of boronic ester- narized architectures. For example, a pair of 2D COFs could
linked LCOFs is given in Scheme 1. be attained with triazatruxene (TAT) as luminescent building
In 2008, Wan et al. reported the first example of LCOFs con- blocks (denoted as TAT-COF-1 and TAT-COF-2), which displayed
sisting of triphenylene and pyrene functionalities that named regular honeycomb lattice. TAT-COF-1 was synthesized under
as TP-COF. The belt shaped TP-COF was synthesized via the solvothermal conditions by condensation of 2-CHO-TAT and
condensation reaction of 2,3,6,7,10,11-hexahydroxytriphenylene benzene-1,4-diamine, while TAT-COF-2 was synthesized by con-
(HHTP) and pyrene-2,7-diboronic acid (PDBA), and showed an densation of 2-CHO-TAT and 2-NH2-TAT. In comparison with
intense blue luminescence at 474 nm (Figure 1).[6] Since then, TAT-COF-1, the TAT-COF-2 displayed highly crystallinity as well
a variety of boronic ester-linked LCOFs with varied topologies as a rapid fluorescence on/off switching nature toward electron
have been reported. For example, a 2D HHTP-DPB COF with rich and deficient arene vapors.[51] Imine-linked LCOFs with
4.7 nm wide hexagonal pores was constructed using HHTP a 3D structure can be attained using 3D topological building
and 4,4′-diphenylbutadiynebis (boronic acid) (DPB) via con- blocks. For example, pyrene-based 3D LCOFs (3D-Py-COF),
densation reaction. The strongly blue fluorescence of both its which adopted a twofold interpenetrated pts topology, could be
powder and film was ascribed to the cofacially packed diphe- constructed via condensation of tetra(p-aminophenyl) methane
nylbutadiyne subunits that extended π-conjugation.[40] Interest- and 1,3,6,8-tetrakis(4-formylphenyl) pyrene. The powders of
ingly, the emissive wavelength could be tuned via controlling 3D-Py-COF displayed an intense yellow green luminescence
the ratios of dehydrobenzoannulenes (DBAs) and PDBA. A under UV light irradiation (Figure 3A).[7] Additionally, dual-
series of colorful LCOFs could be obtained by condensing emissive COFs (denoted as COF TzDa) have been prepared via
PDBA with DBA[12], DBA[18] and a mean value (MV) of both, condensation of 4,4′,4″-(1,3,5-triazine-2,4,6-triyl) trianiline (Tz)
denoted as Py-DBA-COF 1, Py-DBA-COF 2, and Py-MV-DBA- and 2,5-dihydroxytere phthalaldehyde (Da). Their two main
COF, respectively. The Py-DBA-COF 2 powder exhibited blue- fluorescence emissions peaked at 500 and 590 nm, respectively,
greenish luminescence centered at 483 nm, while the powders in common organic solvents were ascribed to the excited-state
of Py-DBA-COF 1 and Py-MV-DBA-COF displayed redshifted intramolecular proton transfer (ESIPT) effect (Figure 3B).[52]

Boronic
acids
Catechol
TP-COF HHTP-DPB-COF Not found BZL-COF
Py-DBA-COF 1 Not found Not found Not found
Py-DBA-COF 2 Not found Not found Not found
Not found Not found Ph-An-COF Not found
Scheme 1. The synthesis of boronic ester-linked LCOFs.
In recent years, a variety of imine-linked LCOFs with different pylphenyl)benzene (iPrTAPB), respectively, in dry dioxane and
topology structures have been successively synthesized, such as acetic acid (Figure 3C).[55] The TAPB-TFP exhibited a broad
COF-hydroxyquinoline,[53] Py-TPE (tetraphenylethene)-COF,[28] emission band at 425 nm upon excitation at 285 nm, whereas
and TPE-COF.[23] iPrTAPB-TFP showed two emission bands centered at 334 and
The imine linkages could further evolve to the β-ketoenamine 455 nm upon excitation at 290 nm. Another example of ketoe-
linkages through an irreversible enol-to-keto tautomerization. namine-linked LCOFs was Bpy-COF, which was prepared via
As shown in Scheme 4, the β-ketoenamine-linked LCOFs is the Schiff base reaction of 5,5′-diamino-2,2′-bipyridine (Bpy)
fully charted. The synthesized β-ketoenamine-linked LCOFs and 2,4,6-triformylphloroglucinol (Tp).[56] Bpy-COF was attained
were featured with a much enhanced acid- and base- stability.[54] in bulk, which could be further exfoliated to nanosheets by
For example, Kaleeswaran et al. synthesized two 2D LCOFs grinding and ultrasonicating. The sheet-shaped Bpy-COF exhib-
(denoted as TAPB-TFP and iPrTAPB-TFP) via condensation ited weak blue fluorescence with an emission band at 370 nm.
of 1,3,5-triformylphluroglucinol (TFP) with 1,3,5-tris(4”-ami- The similar methods of synthesizing β-ketoenamine-linked
nophenyl)benzene (TAPB) or 1,3,5-tris(4”-amino-3”,5”-isopro- COFs have been used in the preparation of various LCOFs,

Figure 1. A) The synthesis of TP-COF. B) The fluorescence image of TP-COF. C) The fluorescence spectra of TP-COF excited at 340 nm (black curve)
and 376 nm (dotted curve) responsively. Adapted with permission.[6] Copyright 2008, Wiley-VCH.
such as mechanochemical COF-TpMA (COF-TpMA (MC)),[57] hydrazide and 1,3,5-triformylbenzene under solvothermal
TRIPTA (condensation product of 1,3,5-tris-(4-aminophenyl) conditions.[60] The COF-LZU8 showed strong blue fluores-
triazine and 1,3,5-triformylphloroglucinol),[58] and COF-JLU4[59] cence both in solid state and in solution. Since then, a series
in Scheme 4. of hydrazone-linked COFs with solid-state photoluminescence
have been synthesized, which exhibited a wide range of emis-
sion colors from blue, green, yellow, and even white (Figure 4).[24]
2.1.3. Hydrazones Their fluorescence wavelength could be tuned by controlling the
spacer length and side-chain functionalities. However, the hydra-
The hydrazone linkages are also developed for construction of zone linkages could partially quench the emission of building
LCOFs, as shown in Scheme 5, via condensation of aldehyde blocks via photoinduced electron transfer (PET) effect. Thus,
and hydrazide in the presence of AcOH catalyst. Ding et al. pre- the elimination of such transfer was considered as an effec-
pared a thioether-functionalized COF (denoted as COF-LZU8) tive way to improve the emission of hydrazone-linked LCOFs.
via the condensation of 2,5-bis(3-(ethylthio)propoxy)terephthalo For example, the hydrazone-linked TFPPy-DETHz-COF, which
Monomers
Ph-COF BPh-COF DBD-COF PPy-COF
TMPh-COF
Scheme 2. The synthesis of boroxine-linked LCOFs through self-condensation.

Figure 2. A,a) The synthesis of 2D colloidal boronate-ester COFs in previous work and b) the synthesis of 2D and 3D colloidal boroxine-linked COFs
in this work. B) The images of COF monomer solutions and corresponding COF solutions under a) natural light and b) UV irradiation. Adapted with
permission.[50] Copyright 2019, American Chemistry Society.
was attained by condensation of 1,3,6,8-tetrakis(4-formylphenyl) 2.1.5. Imides

pyrene (TFPPy) and 2,5-diethoxyterephthalohydrazide (DETHz),
displayed weak green-yellow luminescence centered at 540 nm The imide linkage can be formed via quasi reversible reaction
upon dispersion in tetrahydrofuran (THF).[41] When F− was added, between amine derivatives and acetic anhydride at high tem-
its fluorescence could be remarkably enhanced. The underlying perature (Scheme 8).[47] As shown in Figure 6A, Wang et al. syn-
mechanism was that F− could trigger the deprotonation of N–H thesized two imide-linked LCOFs (denoted as PI-COF 201 and
unit into N− anion and thus eliminate electron transfer effects. PI-COF 202) via directly heating melamine (MA) mixed with
pyromellitic dianhydride or naphthalenetetracarboxylic dianhy-
dride in N2 atmosphere, respectively.[63] PI-COF 201 revealed a
2.1.4. Azines and Triazine cone-shape morphology, whereas PI-COF 202 displayed a block
morphology (Figure 6B). Despite of their different morphologies,
The azine-linked LCOFs utilize the condensation of aldehydes both PI-COFs showed similar strong blue fluorescence. Another
and the shortest hydrazine monomer to construct polygon example of PI-COFs with porous crystalline structure was attained
skeletons.[47] A full list of azine-linked LCOFs is presented in via imidization reaction between tetra(4-aminophenyl) porphyrin
Scheme 6. For example, Li et al. reported a LCOF (denoted as (TAPP) and perylenetracarboxylic dianhydride.[29] Such porous
COF-JLU3) utilizing 1,3,5-tris(3′-tert-butyl-4′-hydroxy-5′-formyl PI-COF, with featured high thermal stability and large surface
phenyl) benzene and hydrazine hydrate as reaction comono- area, showed a strong fluorescence emission peaked at 500 nm.
mers (Figure 5A).[42] The yellow-green powder of COF-JLU3
exhibited a strong orange-red luminescence with an emission
centered at 601 nm when excitation at 424 nm. Besides, Kona- 2.1.6. CC linkages and CC Linkages
varapu et al. prepared the COF-1 structure-like LCOFs via conden-
sation of 2,4,6-tris(4-formylphenoxy)-1,3,5-triazine and hydrazine The CC linkages are formed via the Knoevenagel condensa-
hydrate, which exhibited emission peaked at 450 nm upon excitation of aldehydes and benzyl cyanides with a base as catalyst.
tion at 340 nm.[61] Specifically, the CC linkages could be utilized to construct
Similarly, as shown in in Scheme 7, the covalent triazine-based fully π-conjugated COFs. For example, Jin et al. designed a
frameworks (CTFs) are synthesized through the trimerization series of sp2 carbon-conjugated LCOFs denoted as sp2c-COF,
reaction of nitriles. For example, Ren et al. proposed room tem- sp2c-COF-2, and sp2c-COF-3, respectively.[43] The synthesis
perature and microwave-assisted methods to synthesize CTF-type procedure of these LCOFs were based on polycondensa-
polymers P1-P6 and P1M-P6M. The synthesized CTFs achieved tion of TFPPy as knot with 2,2′-(1,4-phenylene)diacetonitrile
cyclotrimerization of aromatic nitriles upon the trifluorometh- (PDAN), 2,2′-(biphenyl-4,4′-diyl)diacetonitrile (BPDAN), and
anesulfonic acid (TFMSA) as catalyst and all of them showed 2,2′-([1,1′:4′,1′′-terphenyl]-4,4′′-diyl)diacetonitrile (TPDAN),
bright fluorescence.[45] Alternatively, Wang et al. synthesized a respectively, as linkers (Figure 7A). The three LCOFs were
series of novel fluorescent CTFs (denoted as F-CTFs) utilizing phase-dependently emissive and displayed different lumines-
different tetra-cyano compounds as the initial monomers and cence features in solid state and in different solvents such as
TFMSA as catalyst (Figure 5B).[30] The results showed that all of THF, water, and hexane (Figure 7B).
F-CTFs could exhibit strong fluorescence in solid state and their Furthermore, the Knoevenagel condensation could be fur-
emission colors could be tuned from blue (F-CTF1) to yellow ther developed for the construction of CC linked LCOFs.
(F-CTF2) to orange (F-CTF3) as the increasing of conjugation For example, Ozdemir et al. synthesized a CC bonded nano-
chain length (Figure 5C). Additionally, Geng et al. synthesized a porous polymer network (denoted as COP-100) at room tem-
kind of CTF (named TDPDB) by Friedel–Crafts polymerization perature.[64] The COP-100 was formed via knoevenagel-like
reaction of N,N′-diphenyl-N,N′-di(m-tolyl)benzidine (DPDB) with condensation of 1,3,5-benzenetriaceto nitrile and terephthal-
2,4,6-trichloro-1,3,5-triazine (TCT) catalyzed by methanesulfonic dehyde without requiring existence of catalyst (Figure 7C). It
acid.[62] The TDPDB emitted bright cyan fluorescence under UV showed strongly fluorescence but the emission spectrum was
lamp irradiation when dispersed in both dioxane and THF. broad and structureless, with a maximum emission at 420 nm

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Scheme 3. The synthesis of imine-linked LCOFs.
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Scheme 3. Continued.
Small 2022, 18, 2103516

Scheme 3. Continued.
and a shoulder at 484 nm. A full list of CC linked and CC TNP-CHO) via condensation of 4-(bis(4-bromophenyl)amino)
linked LCOFs through Knoevenagel condensation is given in benzaldehyde and tris(4-(4,4,5,5-tetrame-thyl-1,3,2-dioxab-
Scheme 9. Besides, the CC linkages can be formed by Suzuki orolan-2-yl)phenyl)amine at a liquid–liquid interface.[65] The
emulsion polymerization of organic boronic acid derivatives TNP-CHO was further modified with thiosemicarbazone to
with organic halogen compounds under Pd catalysis. He et al. obtain polymer nanoparticles, which could yield bright yellow
prepared a triarylamine-based LCOF nanoparticles (denoted as fluorescence.

Figure 3. A) The synthesis and structure of 3D-Py-COF. Adapted with permission.[7] Copyright 2016, American Chemistry Society. B,a) The synthesis
of TzDa. b) The UV–vis absorption (black) and fluorescence (red) spectra of TzDa, and the fluorescence spectra of TzDa in ethyl acetate with different
water content. Adapted with permission.[52] Copyright 2017, American Chemistry Society. C) The synthesis of TAPB-TFP and iPrTAPB-TFP. Adapted with
permission.[55] Copyright 2015, The Royal Society of Chemistry.
2.1.7. Amine temperature to obtain target product. Notably, the factors such
as solubility, reactivity of building blocks, crystalline nucleation
The amine linkages are mainly formed by condensation of type, and crystalline growth rate are extremely critical for the
amines and cyanuric chloride derivatives.[66] It is an emerging construction of appropriate reaction systems.[68]
linking strategy for LCOFs preparation and limited examples
can be found. For a very recent example, Li et al. constructed a
3D LCOF (denoted as COF-TT) using the bis(tetraoxacalix[2] 2.2.2. Microwave-Assisted Synthesis
arene [2]triazine) core reacted with tetra(p-aminophenyl)methane
through solvothermal method (Figure 8).[67] The COF-TT was Microwave methods have been developed to overcome the dis-
highly porous with the main aperture size of 5.2 Å and structur- advantages of solvothermal methods such as relatively long
ally stable even at 400 °C. Upon excitation at 370 nm, the COF-TT reaction time and high reaction temperature. For example,
displayed the fluorescence emission band centered at 490 nm. Zhang et al. prepared a Schiff base network LCOF (SNW-1)
of micro- and mesoporous nanoparticles by the microwave-
assisted polycondensation synthesis of melamine and tereph-
2.2. Synthetic Methods of LCOFs thalaldehyde in dimethylsulphoxide.[69] SNW-1 nanoparticles
displayed bright fluorescence whether in solid state or in
2.2.1. Solvothermal Synthesis suspension. The P1M-P6M mentioned above were also syn-
thesized through the microwave-assisted polycondensation
Solvothermal method are the most frequently used method synthesis.[45]
for LCOFs preparation.[5,47] Typically, the synthetic methods
start with placing LCOFs precursors, desired solvent or solvent
mixture, and catalysts in the closed reaction vessel such as a 2.2.3. Ambient Conditions Synthesis
sealed pyrex tube. The mixture is sealed with a gas burner after
sonication for a short period and degassing via freeze–pump– The synthesis of COFs at room temperature is believed to
thaw cycles. The reaction is initiated by heating at a suitable be critical especially for fragile building blocks or sensitive

Amines
TFP
TpPa-1 TpPa-2
R=H
R=M BPy-COF
Non-emissive COF-TpMA
Amines
TFP
IPrTAPB-
TAPB-TFP TFP TRIPTA
Scheme 4. The synthesis of ketoenamine-linked LCOFs.
substrates. For example, Zhang et al. proposed a novel buff- example, Liu et al. synthesized the mechanochromic lumines-
ering reaction band (BRB) method for the first time to syn- cent LCOF named COF-TpMA via Schiff base reaction between
thesize fluorescent LCOF crystalline quantum dot (denoted triformylphloroglucinol (Tp) and MA by manual grinding the
as QDCOF).[70] The method acquired a three-phase systems precursors in an agate mortar at room temperature.[57] As the
using three different solvents (from top to bottom are N,N- advance of grinding, the color of the mixture changed from
dimethylformamide, acetic acid, and N,N-dimethylformamide/ milky white to deep yellow then to brownish, while the fluo-
dichloromethane) and yielded two mutually diffusible inter- rescence of the powder changed from yellow-green to yellow
faces among these three phases. Subsequently, the amine mon- then to orange, demonstrating the production of COF-TpMA.
omer tri(4-aminophenyl)amine in top layer and the aldehyde Additionally, the volume of the bulk products increased consid-
monomer 2,4,6-triformylphenol in the bottom layer simultane- erably, which might be related to the material crystallinity and
ously diffused to the middle layer and reacted in the presence morphology changes as a result of the formation of COF-TpMA.
of acetic acid. A large number of small QDCOF particles with
blue-green fluorescence could thus form in ambient conditions.
3. Brightening LCOFs
2.2.4. Mechanochemical Synthesis 3.1. Design Principle
Besides solvent-based synthetic methods, the LCOFs could Luminescent small molecules are the mostly studied and
be prepared through reaction in solid states such as mecha- widely used luminophores. They are usually utilized as models
nochemical synthesis.[5,47] Such preparation route without to describe the luminescence process from the fundamental
solvent is simple, economical, and environmentally benign. For photophysical aspect. Typically, when a luminophore absorbs
Hydra-zides
Aldehydes
Not found TFPB-DHzDR TFPPy-DETHz- COF-JLU4

R=M
Tf-DHz DR COF
(R=M, Pr, All, S)
Not found COF-LZU8 Not found Not found Not found
Not found TTB-COF Not found Not found Not found
DFDM-THz Not found TFPB-THz Not found Not found
Scheme 5. The synthesis of hydrazone-linked LCOFs.
the energy of excitation light, its ground state electrons are very tunability of topological structures and luminescent properties
unstable and transit to the excited state. The unstable excited through rationally designed synthetic chemistry.
electrons tend to release energy and return to the ground state. The emissive building blocks of LCOFs are spatially adja-
The energy releasing mechanisms are mainly divided into two cent (within several Å). Specifically, the 2D LCOFs with flat
pathways, radiative transition, and nonradiative transition. The polymeric sheet-like structure stack in a face-to-face fashion
nonradiation transition is related to energy that finally lost in with strong interlayer π–π interaction. This could easily trigger
the form of heat, which includes internal conversion, inter the rapid dissipation of excitation energy, thus leading to the
system crossing and molecular motions. The radiation tran- aggregation-caused quenching (ACQ) effect and formation of
sition process is luminescence, which releases the energy of less- or nonemissive COFs.[74] Additionally, as aforementioned,
excitons through yielding photons.[71] However, intrinsic draw- the linkages also generate significant impacts on the emis-
backs cannot be ignored, such as low stability, sensitivity, and sion of LCOFs and, for instance, they can quench the emis-
reusability.[47] It is widely acceptable to overcoming these disad- sion through photoinduced electron transfer effect.[56] How to
vantages of small molecules by compiling them into polymeric activate COFs with their intrinsic luminescent properties is
systems. Compared with conventional polymeric systems, challenging. Meanwhile, this challenge is closely related to the
such as conjugated polymers,[72,73] LCOFs are unique for their development of biosensing and bioimaging applications. To
Figure 4. The synthesis of four kind of hydrazone linked LCOFs and corresponding fluorescence emission wavelengths and bandwidths. Adapted with
permission.[24] Copyright 2018, Springer Nature.
design highly efficient emissive COFs, the current COF bright- For example, extending π-conjugation could facilitate elec-
ening strategies can be classified into two ways: increasing trons transitions due to a lower energy difference (ΔE) from
radiation transition and reducing nonradiative transition. π–π* transition, while restriction of intermolecular motions
Aldehydes
Hydrazine
Py-Azine-COF COF-LJU3 COF-1
Scheme 6. The synthesis of azine-linked LCOFs.
could inhibit nonradiation transition and reduce energy dis- generate a novel emission band at a longer wavelength. In
sipation, resulting in known aggregation-induced emission short, the photophysical phenomena of LCOFs are highly in
(AIE) effects. Furthermore, the charge or proton transfer relation with their structures. Rational designs for enhancing
may change the fluorescence emission of monomers or even their emissive performances can be thus explicitly elaborated
Figure 5. A) The synthesis of COF-JLU3. Adapted with permission.[42] Copyright 2016, The Royal Society of Chemistry. B) The synthesis of F-CTFs.
C) The fluorescence images of a) F-CTF1, b) F-CTF2, and c) F-CTF3. d) The UV–vis spectra of F-CTFs. e) The fluorescence spectra of F-CTFs in solid
state powder. Adapted with permission.[30] Copyright 2016, Wiley-VCH.
Monomers
P1/P1M P2/P2M P3/P3M P4/P4M P5/P5M
Monomers
F-CTF2 F-CTF3
P6/P6M F-CTF1
Scheme 7. The synthesis of luminescent CTFs through self-condensation.
by selection of building blocks and construction of structural could be excited easier compared with saturated counterparts,
connections. accompanied by a redshifted λmax.[75] The correlation between
the radiative rate constant (kr), radiationless rate constant (knr),
and the π conjugation length in the excited singlet state have
3.2. Selection of Building Blocks been investigated by Yamaguchi et al.[76] Their results showed
that the tendency of kr/knr value increased as the extension of
Building blocks of LCOFs intrinsically are constructive lumi- π conjugated molecule, indicating that π-conjugation extension
nophores. Currently, more considerations come from how to might be beneficial to the fluorescence emission of the chromo-
reduce or eliminate ACQ effects. Molecular designs of building phores. Thus, the LCOFs with large π-conjugated building
blocks usually are undertaken through modification of lumines- blocks such as TAT-COF-2,[51] COF-LZU8,[60] PI-COF 201, and
cent small molecules, including enlargement of monomers with PI-COF 202[63] showed luminescence upon UV irradiation
highly π-conjugation structure and introduction of flexible long because they could reduce energy consumption during vibra-
chains, or use of ACQ-free luminophores, including AIE lumi- tional relaxation.
nogens (AIEgens) and luminophores with charge transfer pairs.
3.2.2. Flexible Building Units

3.2.1. Large π-Conjugation Building Blocks
The introduction of flexible building units can adjust the π–π
π-Conjugation is beneficial for π–π* transition, which have stacking interaction between layers and largely reduce the ACQ
a much lower energy gap (Egap) than that of σ–σ* transition. effects, resulting in the luminescence increase of LCOFs. For
Thus, the organic luminophore with π-conjugation structure example, the bulky tert-butyl groups could reduce the interlayer
Acetic anhydrides
Amines
PI-COF-201 PI-COF-202 Not found
PI-COF
Not found Not found
Scheme 8. The synthesis of imide-linked LCOFs.
π–π interaction in COF-JLU3, thus leading to higher lumines- sive LCOFs are utilize AIEgens as building blocks into LCOFs
cence efficiency.[42] For another example, Li et al. synthesized preparation.[82]
a novel 2D LCOF (denoted as DTZ-COF) via condensation of One of most-used AIEgens in LCOF fabrication is TPE.
2,4,6-tris(4-formylphenoxy)-1,3,5-triazine (TPOT-CHO) and When TPEs are linked and piled into assembly buildings,
2,4,6-tris(4-aminophenyl)-1,3,5-triazine (TPT-NH2).[77] The excel- their twisted propeller-like shape units, which are free from
lent emission performance of DTZ-COF was attributed to π–π stacking interaction, are immobilized and block the non-
the introduction of flexible monomer TPOT-CHO to mitigate radiative decay, giving rise to the fluorescence emission of
the ACQ effect. Similarly, the introduction/extension of alkyl TPE-COFs.[81] For example, Dalapati et al. designed the first
groups on the side of building blocks can increase the inter- AIE-based LCOF named TPE-Ph COF by integrating TPE units
layer space of planarized LCOFs and this strategy has been uti- into the polygon vertices.[83] The quantum yield of TPE-Ph
lized to attain COF-4-OH with high quantum yield.[78] COF could reach as high as 32% in the solid state. Since then,
a series of TPE-based LCOFs have been developed, including
3D-TPE COF,[23] porous covalent triazine-based framework
3.2.3. AIEgens (PCTF-8),[22] Py-TPE-COF,[28] and National University of Singa-
pore (NUS) 30–32 nanosheets.[84] Their bright emission can be
AIEgens are molecules with the AIE effect, which has been attributed to the framework-induced inhibition of TPE motion.
found and well studied by Tang’s group since 2001.[79,80] The Nitrile groups with twisted conformation could also be uti-
typical AIEgens are nonemissive in the dispersed state, but lized as AIEgens in the construction of LCOFs buildings. Spe-
intensively luminescent in the aggregate form.[79,81] The aggre- cifically, the nitrile groups can serve as electron acceptors (A).
gate forms include ordered aggregates, endowing AIEgens to Upon introduction of electron donors (D), they can be used to
naturally fit the construction of LCOFs. The emission mecha- fabricate simple D–A systems, yielding tunability of photophys-
nism of AIEgens can be explained by restricted intramolecular ical features.[81] For example, the emissive colors of sp2c-COFs
rotation (RIM) process. RIM effects usually refer to the restric- could be tuned via changing the length of their arylene vinylene
tion of intramolecular rotations (RIR) and vibrations. After two linkers.[43] Twisted angles of their nitrile group were accordingly
decades of effort, the library of AIEgens has been extensively changed, altering the degree/density of the π electron cloud
enriched. Thus, as an inverse effect, the straightforward overlap between neighboring segments as well as the overall π
strategies to eliminate the ACQ effects and obtain highly emis- conjugation over the 2D skeletons.
Figure 6. A) The synthesis of PI-COF 201 and PI-COF 202. B) The scanning electron microscope images of (top panel) PI-COF 201 and (bottom panel)
PI-COF202. Adapted with permission.[63] Copyright 2017, The Royal Society of Chemistry.
Figure 7. A) The synthesis of sp2c-COF, sp2c-COF-2, and sp2c-COF-3 and corresponding reconstructed crystal structure of single layers and many layers.
B) The solid state absorption spectra (black curves) and fluorescence spectra (red curves) of a) sp2c-COF, b) sp2c-COF-2, and c) sp2c-COF-3. d) The
fluorescence images of sp2c-COF, sp2c-COF-2, sp2c-COF-3, model compound, and TFPPy monomer in water dispersion. Adapted with permission.[43]
Copyright 2018, Springer Nature. C) The synthesis of COP-100. Adapted with permission.[64] Copyright 2015, The Royal Society of Chemistry.
Aldehydes
Benzyl
cyanides
sp2c-COF Not found Not found
sp2c-COF-2 Not found Not found
sp2c-COF-3
Not found Not found
TFPT-BTAN COP-100
Not found
Scheme 9. The synthesis of LCOFs through Knoevenagel condensation.
3.2.4. Excimer Molecules and hydroxyquinolines, also have luminescence properties.[93–97]

Their monomers can be efficiently dimerized through irradiation
Excimers, as charge transfer complexes which could lead to and form excimers, giving rising to luminescence.
the emission peak of chromophores, are formed as a dimer Intramolecular charge transfer (ICT) emerges, when the
between the same species (A and A*), which encountered in an luminophore simultaneously contains both D and A linked by
electronic excited state and dissociated in its ground electronic a conjugate bridge.[98] During the exciting process, exciplexes
state. [85] Among excimer molecules, pyrene is usually utilized are formed by interaction of D (or A) molecules in excited state
for the construction of LCOFs, due to its featured long excite denoted as D* (or A*) with its counterpart in ground state A
state lifetime and large Stokes shift.[86–91] Pyrene-based LCOFs, (or D). Interestingly, the formation of intramolecular exciplex
such as PPy-COF,[25] Py-Azine COF,[92] and 3D-Py-COF,[7] can could form an extra ICT state and generate redshifted fluores-
yield bright luminescence, due to the formation of pyrene cence emission band, compared to the local excited state emis-
excimers. Additionally, COFs with monomers, such as anthracenes sion band.[99] For example, the emission band of COF TzDa
Figure 8. The synthesis and structure of COF-TT. Adapted with permission.[67] Copyright 2019, The Royal Society of Chemistry.
located at 500 nm was ascribed to the ICT between the electron layered COF nanosheets TfpBDH-CON obtained via simple
donor phenyl group to the electron acceptor triazine of the Tz liquid phase exfoliation method was almost 90 times higher
moiety.[52,100] than that of their bulk state.[104] Similarly, a series of nanosheets
exfoliated from layered LCOFs, such as sp2c-CON-2 and sp2c-
CON-3,[43] PI-CONs,[29] ethidium bromide (EB)-TFP-iCONs,[105]
3.3. Administration of Intra/Intermolecular Interactions and CCOF 7-nanosheets,[20] have found their much enhanced
fluorescence compared to their corresponding bulk COFs.
Intra/intermolecular interactions among the monomers main- The models of piling layers also matter the optical properties
tain the stability of COF structures and corresponding physico- of planarized LCOFs. When the form of AA-eclipsed stacking
chemical properties. They can exert a crucial role in brightening is changed to AB-staggered stacking model, the π electrons
LCOFs, due to their bridge functions to connect the electrons between layers are dislocated, resulting in weakening interlayer
of neighbor monomers. Intra/intermolecular interactions of π–π interactions. Therefore, the AB-staggered stacking can
LCOFs involve not only concrete covalent bonds but also weak significantly decrease the ACQ effect and promote the fluores-
intermolecular interactions such as π–π interactions, hydrogen cence emission of LCOFs. For example, the dual-pore COF-1,
bonds. Currently, the efforts to regulate the molecular interac- 4′-(bis(4-formylphenyl)amino)-[1,1′-biphenyl]-3,5-dicarbaldehyde
tions have been undertaken, including adopting fully conjugated (BABD)-1,4-diaminobenzene (DB) and COF-BABD-benzidine,
CC linkages, exfoliating bulk COFs to nanosheets, acquiring adopting staggered stacking mode, could exhibit green emis-
AB-staggered stacking mode and introducing hydrogen bonds. sion.[27] Instituto Madrileno de Estudios Avanzados-COF-1 as
another example of staggered arrays of the pyrene units, could
exhibit layer-packing-driven green fluorescence in solid-state,
3.3.1. π-Conjugation Linkages as a result of weakened π–π stacking interaction and then the
inhibition of nonradiative energy dissipation.[106]
Differently from the saturated linkages, such as boronic ester Another interesting approach to increase appropriate inter-
with weak π-electron delocalization, the CC linkage of sp2 molecular distance was the embedment of small molecules
carbon frameworks allows for the formation of fully conjugated between layers, such as solvent molecules, resulting in light on
systems.[1] For example, the bright luminescence properties of or enhancing the emission of LCOFs. For example, the BZL-
CC linked LCOFs such as TP-COF-AO,[101] COF-PDAN-AO,[102] COF showed completely nonluminescent at ambient condi-
and 2,4,6-tris(4-formylphenyl)-1,3,5-triazine-2,2′,2′-(benzene- tions. Its photoluminescence (PL) properties could be activated
1,3,5triyl)triacetonitrile-amidoxime (TFPT-BTAN-AO),[103] were through inserting solvent molecules (dioxane) between its 2D
resulted from their highly stable π-conjugated skeleton. polymeric layers, forming Dioxane⊂BZL-COF. The introduc-
tion of small molecules increased the interlayer distance from
3.4 to 3.7 Å, thus activated the PL of BZL-COF with bright
3.3.2. π-Stacking Reduction yellow phosphorescence.[49]
In order to overcome the thermal decay of excited states induced

by strong π–π interaction, exfoliation of stacked COFs to obtain 3.3.3. Hydrogen Bonds
nanosheets is a feasible approach for enhancing emission of
LCOFs without affecting their molecular structure and crystal- The introduction of intra- and interlayer hydrogen bonds has
line phase. For example, the fluorescence intensity of the thin considerable functions and benefits for light up the LCOFs.
Figure 9. A) The mechanism of ESIPT process. Adapted with permission.[109] Copyright 2018, The Royal Society of Chemistry. B) The form of IISERP-
COF7 in i) pyridine, ii) THF, and iii) NMP, respectively. Adapted with permission.[9] Copyright 2018, American Chemistry Society.
On one hand, hydrogen bonds, as restrain forces, facilitate 3.4. Learning from Other Luminescent Porous Materials
to inhibit rotation of AIEgen monomer moieties and trigger
radiative energy decay.[107] Li et al. proposed a strategy to Compared with other luminescent porous materials such as
synthesize hydrazone-based COFs with the high lumines- luminescent porous organic polymers (POPs) and luminescent
cence in solid-state through molecule design.[24] The intra- metal–organic frameworks (MOFs), the studies of LCOFs
and interlayer hydrogen bonding and eclipsed stacking in start relatively late. Strategies that generate or promote the
the COFs could strengthen RIR effects and render the energy emission of LCOFs could be borrowed from those neighbor
release from nonradiative to radiative pathway, give rise to and vigorous fields. For one thing, π-electronic compounds
bright emission. that can be used as the building blocks in LCOFs are limited,
On the other hand, the intra- and interlayer hydrogen bonds due to the quenching effects of π-stacking. However, with
can yield the unique COF-triggered ESIPT luminescent mecha- respect to luminescent POPs, the majority of π-electronic
nism, forming dual-emitting luminescent system. ESIPT is a materials can be used as the emissive core. The route of con-
phototautomerization involving the proton transfer from the structing luminescent POPs is expected to inspire the design
intramolecular hydrogen bond donor (OH, NH2) to the of LCOFs based on π-electronic monomers. POPs are amor-
hydrogen bond acceptor (CO, CN) less than 2 Å away, phous porous polymers with 3D crosslinked π-network struc-
which is depended on a pre-existing six- or five-membered ring tures.[107] Such 3D network model can considerably eliminate
hydrogen bonding configuration. As shown in Figure 9A, the the π-stacking effects, guaranteeing sufficient quantum yields
ESIPT molecules can yield an extra redshift emission from of π-electronic materials.[110] Therefore, construction of LCOFs
enol forms as a result of a rapid four-step conversion from the in the 3D network form might be a promising approach to
enol (E–E*) to the keto (K–K*) upon photoexcitation.[1,108,109] involve more π-electronic monomers into the portfolio of
For example, COF-4-OH displayed dual fluorescence emission LCOFs. For another thing, similarity of luminescent designs
bands at 400 and 590 nm. The emission band at 400 nm was could be found in both luminescent MOFs and LCOFs, such
originated from the fluorescence of enol state, while the band as utilization of luminescent monomers to construct frame-
at 590 nm was ascribed to the ESIPT emission.[78] Besides, the work and material nanominiaturization.[111] However, the
weak interactions of hydrogen bonds are sensitive to environ- relatively versatile coordination interactions enable MOFs
ment changes, rendering the emissions of ESIPT luminophores featuring desirable pore structure to be promising candi-
responsive toward exogenous stimuli. Solvent is found to be a dates for luminescent nanoparticle immobilization through
significant factor to alter the emission of ESIPT molecules. For rational design.[112] Technologies for encapsulating nanoparti-
example, when suspended in N-methyl-2-pyrrolidone (NMP), cles into MOFs, including the representative “ship-in-bottle”
Indian Institute of Science Education and Research Pune strategy, i.e., loading precursors of nanoparticles to presynthe-
(IISERP)-COF7 could yield red-green emission, resulting from sized MOFs cavities followed by in situ synthesis, or “bottle
the keto-enol tautomerism between the resorcinol units and around ship” strategy, i.e., epitaxially growing MOFs outside
the CHN.[9] The solvent NMP could stabilize keto and nanoparticles modified by ligands with affinity to metal core or
enol forms in a near 50:50 ratio. Interestingly, when the N− skeleton molecules of MOFs, can confine luminescent nano-
donor solvents such as pyridine could stabilize the keto form of materials in the framework of MOFs, generating multifunc-
IISERP-COF7 and thus redshift its emission to yellowish-orange tional luminescent composites.[113] Such series of strategies
via proton transfer from the enol to the Schiff nitrogens. On the largely extend the concept and scope of luminescent MOFs.
contrary, the O-containing solvents such as THF could stabi- Therefore, the development of hybridization technologies with
lize the enol form via hydrogen bonding to enol moieties and luminescence species should be of great potentials to produce
cause the blueshifted emission of IISERP-COF7 to blue-green intriguing and powerful LCOFs. The design of such lumines-
(Figure 9B). cent composites might be directed toward to the improvement
of pore microenvironments of COFs to allow precursors to 4.1.2. Hg2+ Sensors

preserve, or the development of mild methods of covalent
bonding to avoid exposure of luminescent materials toward Hg2+ as one of the most toxic heavy metals has been acknowl-
harsh preparation conditions of COFs. edged related to the dysfunction of the immune system, the
central nervous system and organs such as lungs, kidney,
skin, and eyes.[122] To detect trace Hg2+, a privileged iono-
4. The Application of LCOFs in Biosensing phoric receptor for Hg2+, sulfur group, has always been used
in LCOF-based sensor design, because of its distinct π-donor
LCOFs are promising and attractive photoluminescent materials character and specific affinity.[123,124] For example, the thioether-
in biosensing application due to their advantages of responsive based COF-LZU8 showed fluorescence quenching against Hg2+
luminescence, tunable structural designs for molecular recogni- through the electron transfer with a detection limit of 25.0
tion, and porous nature to allow the enrichment and removal ppb.[60] On the other hand, the high affinity between sulfur
of analytes. The most-used mechanisms of LCOFs in fluores- and Hg2+ hampered the renewability of the corresponding sen-
cence detection are mainly ascribed to host–guest interactions sors. To improve recyclability of sensors, Cui et al. synthesized
that could trigger energy or charge transfer between LCOFs a nitrogen-based COF (denoted as TFPPy-CHYD) with bright
and analytes, leading to the change of luminescence properties luminescence for simultaneous detection and adsorption of
of LCOFs. Alternatively, the aggregation of nanosized LCOFs Hg2+.[44] The flexible carbohydrazide (CHYD) linkage unit inte-
induced by analytes could also change the emission of LCOFs. grated in the extended skeleton served as a specific yet revers-
ible binding receptor for Hg2+. Therefore, the TFPPy-CHYD
showed good selectivity with an ultralow detection limit of 17 ×
4.1. Detection of Metal Ions 10−9 m and excellent regenerability for Hg2+.
Mineral ions, such as Fe3+, Hg2+, Al3+, and Cu2+ could par-
ticipate in the regulation of human homeostasis balance, and 4.1.3. UO22+ Sensors
abnormal level of them may cause severe diseases and damage
to human organs.[114,115] Besides, some heavy metal ions, such UO22+ as a kind of radioactive heavy metal oxides has been
as UO22+, Au3+ could penetrate into environment and will even- widely utilized in a variety of power plants and military equip-
tually accumulate in the human body, causing heritable adverse ment. However, the UO22+ penetration caused by the wide-
effects on human health.[116,117] Therefore, it is of importance to spread usage of nuclear power and improper disposal of
develop sensors for different metal ions in varied scenes. nuclear wastes could trigger severe radiation damage to human
organs including kidneys, livers, and bone.[103,116,125] Therefore,
it is necessary to find effective methods for simple and rapid
4.1.1. Fe3+ Sensors detection of UO22+. Zhang et al. utilized the blue-green-emit-
ting QDCOF prepared by the BRB method mentioned above to
Fe3+ as the most abundant transition metal, could participate rapidly detection UO22+.[70] The QDCOF showed obvious fluo-
in various of biological processes at the cellular level including rescence quenching upon addition of uranyl ion with a detec-
oxygen transportation, enzymatic reaction, DNA, and RNA tion limit of 28.6 ppb. The sensitive quenching was ascribed to
synthesis.[118] Whereas, either deficiency or overload of Fe3+ the disruption of large conjugated system through coordination
both could trigger disorders of cellular homeostasis and some interaction between UO22+ and the carbonyl oxygen and sec-
physiological diseases such as diabetes, liver injury, Parkin- ondary amine in keto-form. For another example, TFPT-BTAN-
son’s disease, and cancer.[119,120] Therefore, the determination of AO was utilized for regenerable and real-time monitoring of
Fe3+ whether in the environmental samples or in the human UO22+, due to the high binding affinity and excellent revers-
body has been an important part in human health monitoring. ibility between amidoxime of TFPT-BTAN-AO to UO22+.[103] The
Fe3+ has been known as a benign energy/electron receptor fluorescence intensity of TFPT-BTAN-AO could be quenched in
and can directly quench the emission of certain LCOFs, due the presence of UO22+ through the PET process. This sensing
to its unsaturated outer-most orbits. For example, the PI-COF probe of UO22+ had not only an ultralow detection limit of
201 and PI-COF 202 could achieve highly sensitive detection 6.7 × 10−9 m with an ultrafast response time of 2 s but also an
of Fe3+ with detection limits of 0.13 × 10−6 and 0.22 × 10−6 m exceptional adsorption capacity of 427 mg g−1.
respectively, due to the energy transfer from the COF donor
to receptor Fe3+.[63] The COF-TT also displayed pronounced
fluorescence quenching upon addition of Fe3+ ascribed to the 4.1.4. Al3+ Sensors
PET via Lewis acid–base interaction.[67] Besides, the COF ben-
zene-1,3,5-tricarbohydrazide (Bth)-Dma could also be a “turn- As the most abundant metallic element in the crust, Al3+ has
off” fluorescence sensor of Fe3+ in aqueous solution with a been widely applied into industry and daily life. However, this
detection limit of 0.17 × 10−6 m. The sensing mechanism was situation is followed by increased exposure of Al3+ toward our
ascribed to the strong coordination interaction between Fe3+ environment and living systems. The excess levels of Al3+ may
and the predesigned O,N,O′-chelating sites in the pore wall be related to many central nervous system diseases including
of Bth-Dma, thus leading to fluorescence quenching through Alzheimer’s disease, Parkinson’s disease, and dialysis enceph-
energy or electron transfer.[121] alopathy. Therefore, the efficient and precise detection of Al3+
has been regarded as an imperative task for guarantee of envi- tion. A gradual color change of Au/TTB-COF from the light
ronment and human health.[126–128] Differently from the fluores- yellowness of Au3+ to the brownness of TTB-COF could be
cence quenching mechanisms for detection of other metal ions, observed, suggesting that the TTB-COF could also be utilized to
the detection of Al3+ via Bpy nanosheets was depended on the enrich Au3+ at low concentrations from water.
coordination between Bpy nanosheets and Al3+ to eliminate the
fluorescence quenching process caused by PET mechanism.[56]
Therefore, the Bpy nanosheets as a “turn-on” nanoprobe 4.2. Detection of Small Molecules
showed linearly enhancing fluorescence with increasing Al3+
concentration, and reached equilibrium at 350 × 10−6 m with a 4.2.1. Analysis of Drug Use
15.7-fold enhanced fluorescence.
Amino acids have been acknowledged as the indispensable pre-
cursors for the synthesis of modern medicine.[140] For example,
4.1.5. Cu2+ Sensors the well-known amino acid drug named L-dopa was developed
for the treatment of Parkinson’s disease.[141] In the previous
Cu2+, as one of the most abundant essential transition metal research, the restriction of AIEgens in confined 2D COFs could
ions, plays a vital role in human and biological systems. The be used for the signal amplification of molecular recognition
intake deficiency of Cu2+ will cause several neurodegenera- and sensing.[142] Therefore, Dong et al. utilized NUS 30–32
tive diseases such as Alzheimer’s disease, Wilson’s disease, nanosheets containing long conjugated TPE units for recog-
Menkes syndrome, and amyotrophic lateral sclerosis, while nition of amino acids and small pharmaceutical molecules,
the excessive Cu2+ level in body may related to gastrointestinal such as L-dopa.[84] Compared with their corresponding 3D bulk
disturbance, liver, or kidney damage. Therefore, the detection COF powder, NUS 30–32 nanosheets could respond more rap-
of Cu2+ in biological samples or environment has attracted idly and sensitively through energy transfer in the presence of
much attention.[129–131] For example, Cai et al. designed emis- a series of amino acids and L-dopa.(Figure 10). Moreover, the
sive COFs by amine-aldehyde reaction of MA with paraform- augment of the content of azine moieties in the COF struc-
aldehyde (PA), and phen-aldehyde polycondensation using tures could be beneficial to promote the binding affinity toward
phenol and PA.[132] Interestingly, they introduced hollow amino acids.
Q-Graphene (QG) into such one-pot reactions to obtain QG- The fluoroquinolone drug levofloxacin could be an effec-
scaffolded COFs. The fluorescence intensity of QG-scaffolded tive therapeutic agent for antibacterial infections of human
COFs was found to be about 1.5-time higher than that of pure and animals. While the rampant use of levofloxacin may
COFs, likely due to high ratio of folded edges and surface increase the risk of adverse symptoms like heart disease
defects of QG. The QG-scaffolded COFs could be developed and muscle wasting.[143,144] Wang et al. synthesized a stable
to probe Cu2+ in blood and wastewater. The sensing mecha- Eu3+-modified COF hybrid material (denoted as Eu@TpPa-1)
nism was mainly attributed to chelation between Cu2+ and to sense levofloxacin in serum and urine systems.[145] The
the inherent aminals (NHCH2NH) of MA-PA compos- introduction of Eu3+ not only changed the weak emissive
ites to cause the agglomeration of the COFs. Moreover, the TpPa-1 COF to strong emissive Eu@TpPa-1, but also played
Phen-PA resin of QG-scaffolded COFs was also facilitated to a bridge role in sensing system. After the addition of levo-
absorption of Cu2+ and fast agglomeration of the COFs. These floxacin, the β-diketone moiety of levofloxacin could coordi-
two interactions synergistically quench the emission of the nate with Eu3+ and the energy absorbed by β-diketone was
LCOF probe. For another example, the luminescent COFs-DT then transferred to Eu3+, thereby mainly showing the charac-
showed excellent response to Cu2+ with a low detection limit teristic emission of Eu3+. Upon the removal of levofloxacin,
of 0.076 × 10−6 m.[133] The quenching mechanism was ascribed the emission band of the solution could return to the posi-
to the PET process from the COFs-DT to Cu2+ through the tion of the original TpPa-1. Additionally, the emission of this
coordinate interaction between Cu2+ and the bidentate ligand sensor shifted fast (within 1 min) from bright pink-white to
sites of COFs-DT. yellow as the response toward the decrease of levofloxacin
concentration.
4.1.6. Au3+ Sensors

4.2.2. Detection of Reactive Redox Species
The high affinity between Au3+ ions and DNA or several
enzymes in human body could cause liver, kidney and nervous Hydroxyl radicals (•OH) are regarded as one of the most reactive
system damage.[117,134] However, few efforts have been devoted and harmful reactive oxygen species (ROSs), which have a short
on the selective detection and separation of Au from ultralow lifetime (approximately 10−9 s) and broad responses to biomol-
concentration aqueous solution due to the requirements of sen- ecules such as DNA bases, lipids, and proteins. The important
sitive response and specific affinity to Au3+.[135–138] For example, links to various diseases and the potentials of cancer treatment
the thioether-functionalized COF (TTB-COF) could be applied have spurred the development of the sensing technologies for
for selectively sensing Au3+ in water with a detection limit of •OH detection.[146] For example, Liu et al. developed a sensi-
1.39 × 10−6 m, because of the strong and selective affinity of its tive approach for detection of •OH, utilizing the COF-TpMA.[57]
sulfur group toward Au3+.[139] Moreover, the Au-loaded TTB- The weak absorption strength of COF-TpMA at 283 nm
COF could release Au3+, when treated with Na2S aqueous solu- increased linearly with the addition of •OH (0–15 × 10−6 m),
Figure 10. A) The chemical structures of several amino acids. B) The Stern–Volmer plots of 1,1,2,2-tetrakis(4 formyl-(1,1′-biphenyl))-ethane,
1,1,2,2-tetrakis(4-(N-methylene-aniline)-(1,1′-biphenyl))ethane, and NUS 30–32 nanosheets with the presence of L-phenylalanine. C) The fluorescence
spectra of NUS-30 nanosheets upon titration with the increased L-dopa concentration. D) Ksv constants of NUS 30–32 nanosheets with addition of
amino acids and L-dopa. Adapted with permission.[84] Copyright 2018, American Chemistry Society.
and the corresponding solution displayed apparent color TpPa-1@light-emitting (LE) by introducing triethylamine in order
change from colorless to brown. On the other hand, the emis- to eliminate the nitrogen-related fluorescence quenching.[36]
sive intensity of COF-TpMA at 530 nm was reduced linearly Upon adding MGO into the TpPa-1@LE system, the fluorescence
with the increasing concentration of •OH (0–10 × 10−6 m), emission of TpPa-1@LE shifted from green emission at 476 nm
which was attributed to the electron transfer of •OH to the to yellow emission at 525 nm. This emission shift was ascribed
π-conjugation framework. to the generation of luminescent intermediate exciplex. There-
H2S has been recognized as the third fundamental endog- fore, the fluorescent sensor TpPa-1@LE could quantitatively trace
enous signaling molecule besides nitric oxide (NO) and MGO in serum system with the detection limit of 117.5 × 10−9 m.
carbon monoxide (CO). The abnormal level of H2S in cells
has been linked to various diseases such as Alzheimer’s
disease, Down’s syndrome, diabetes and liver cirrhosis. 4.3. Detection of Biomacromolecules
Additionally, H2S is increasingly known as the biomarker
and therapeutic target for cancer diagnosis such as ovarian, Biomacromolecules like nucleic acids, proteins and polysac-
breast, and colorectal cancers.[147–149] Wang et al. developed charides as important component of organism could mediate
a nanoprobe denoted as 1,3,5-triformylphloroglucinol ami- fundamental biological processes in human body and link to
nosalicylhydrazide (TpASH)-4-amino-1,8-naphthalimide disease initiation and progression as biomarkers. Therefore, the
derivative (NPHS) for H2S sensing by connecting imine- detection of biomacromolecules could be as a routine diagnostic
linked COF TpASH with the two-photon-emitting fluorescent basis for specific diseases.[151,152] Mal et al. utilized EB-TFP-
NPHS.[39] The ultrathin nanosheets of TpASH-NPHS was iCONs to label-free detect double-stranded DNA (dsDNA).[105]
obtained via solvent-assisted exfoliation. Upon the addition of The EB-TFP-iCONs reassembled in the presence of dsDNA
H2S, the fluorescence emission at 535 nm of TpASH-NPHS and caused the generation of hybrid EB-TFP-iCONs-DNA crys-
nanosheets could be enhanced, because of the reduction of talline nanosheets, which lead to enhanced fluorescence from
the azide units with quenching effects to amino groups. 510 to 600 nm. The detection mechanism was attributed to the
Methylglyoxal (MGO), as one of reactive carbonyl species disturbance of excited-state proton transfer to water caused by
(RCSs), has been recognized as an emerging biomarker for hydrophobic environment of EB-TFP-iCONs-dsDNA. This nan-
diabetes mellitus diagnosis.[150] Recently, Wang et al. converted oprobe could sensitively recognize mismatched sequences even
the weak emissive TpPa-1 COF to green light-emitting material ten-base-pair mismatch sequences.
Figure 11. A) The localization imaging of cellular nucleus in HeLa cells using TTA-DFP CONs. Adapted with permission.[153] Copyright 2018, The Royal
Society of Chemistry. B) The comparison of two-photon fluorescence imaging (upper) and single-photon fluorescence imaging (down) of TPI-COF
against 4T1 cells. Adapted with permission.[154] Copyright 2019, Wiley-VCH. C) The interference-resistant imaging of TpASH-NPHS probe in live cells.
Adapted with permission.[39] Copyright 2018, The Royal Society of Chemistry.
5. The Application of LCOFs in Bioimaging another example, Zeng et al. designed the two-photon induction
(TPI)-COF using the benzothiadiazole as chromophore, which
The complex environment of living organisms is always an could be used as enhanced imaging agents for two-photon fluo-
important challenge to the selectivity of conventional small- rescence cell imaging.[154] The intake experiments of TPI-COF on
molecule fluorescent probes in bioimaging. The LCOFs have normal (3T3) and cancer (4T1) cells line demonstrated the good
unique features beneficial for bioimaging, such as predesigned biocompatibility and cell viability even upon 808 nm laser irradia-
topological structure, engineered internal pore surface, excel- tion. Such TPI-COF with high two-photon fluorescence and high
lent biocompatibility, and hypotoxicity. They can be designed photostability could be a desired candidate for in vivo two-photon
to shield from interference components of surroundings, laser confocal scanning microscopy imaging (Figure 11B).
achieving sensing accuracy toward targets.[39,153] Furthermore, The LCOFs can also be applied for sensing of small mole-
the COF nanosheets exfoliated from bulk materials have cules through cell imaging. For example, the TpASH-NPHS
enhanced luminescence, limited photobleaching, high stability could be utilized for endogenous H2S sensing with low back-
in solution and benign dispersibility within the cell. Thus, they ground fluorescence in cells after uptake through clathrin-
have found many applications in bioimaging.[153] dependent endocytosis. (Figure 11C) Notably, the sensing pro-
cess was not jeopardized by both haphazard interaction with
endogenous enzymes and photodegradation.[39] For another
5.1. Cell Imaging example, the COF-TpMA probe existed in the cytoplasm was
endowed with sufficient membrane permeability and moderate
Das et al. synthesized the TTA-DFP-COF via the condensation biocompatibility. The probe could achieve detection of exog-
of 2,6-diformyl-pyridine (DFP) with 4,4′,4′′-(1,3,5-triazine-2,4,6- enous •OH in living systems, when incubated with Baby Ham-
triyl) trianiline (TTA).[153] The bulk COFs then underwent 30 min ster Kidney cells.[57]
exfoliation under microwave irradiation to obtain ultrathin
nanosheets (TTA-DFP CONs). The TTA-DFP CONs showed a
maximum emission peak at 435 nm upon excitation at 375 nm. 5.2. In Vivo Imaging
The small TTA-DFP CONs were used for label-free selective local-
ization of cellular nucleus through clathrin-mediated endocytosis. Compared to the single-photon fluorescence imaging, the two-
They exhibited better biocompatibility without hampering the photon probe could be more suitable for fluorescence imaging
cell architecture and viability, better photosensitivity, more facile in deep tumor tissues attributed to the minimization of tissue
synthesis, and lower cost, when compared to traditional organic autofluorescence and enhanced penetration depth.[39] Further-
or peptide-based nuclear staining dyes. Therefore, this intrinsi- more, tumor cells can secrete more vascular osmotic factors
cally luminescent covalent organic nanosheets material could than normal cells, resulting in enhanced vascular permeability
be a promising nuclear probe for bioimaging (Figure 11A). For and retention (EPR), which is considered to be beneficial for
Figure 12. A) Schematic illustrating of tumor imaging in vivo using TPI-COF. B) The fluorescence imaging of TPI-COF at 4T1 tumor xenograft in Balb/c
mice model (B1, phosphate buffered saline group; B2, TPI-COF group). C) The two-photon fluorescence intensity and D) imaging of TPI-COF at dif-
ferent tumor tissue depth. Adapted with permission.[154] Copyright 2019, Wiley-VCH.
nanomaterials to penetrate blood vessels and accumulate in The composite did not show a fluorescence signal (“off” state)
tumor cells.[155] during blood circulation (pH = 7.4) due to the ACQ effect.
For example, the two-photon fluorescent nanoprobe TpASH- Whereas in tumor cells (pH = 5.5), the composite displayed
NPHS could be applied for H2S imaging in HepG2 tumor tissues an obvious fluorescence signal recovery (“on” state), as a result
even at greater penetration depths in range of 50–250 µm.[39] of the decentralized state of ZnCOF. Simultaneously, the shed
The TpASH-NPHS could also be capable of imaging the early- BSA-coated AuNPs amplified the fluorescence signal through
stage cirrhosis of mouse. During this stage, H2S expression was the generation of a localized surface plasmon resonance effect
up-regulated and could be regarded as the biomarker for the on the surface of the AuNPs. Therefore, those features ensured
early diagnosis of early-stage cirrhosis. For another example, the the hybridized nanoprobe to realize fluorescence imaging for
TPI-COF could yield a very bright dot-like fluorescent signal in a cancer diagnosis with a high signal-to-noise ratio. More impor-
4T1 tumor xenograft of Balb/c mice model and almost no back- tantly, the nanosheets could accumulate on tumor sites via the
ground noise was detected.[154] The maximum detectable depth EPR effect, and when irradiated with NIR, the temperature on
could reach up to around 150 µm (Figure 12). the tumor surface rapidly increased due to their excellent pho-
LCOFs can hybridize with other functional materials tothermal conversion properties. (Figure 13)
through rational designs and the integrated composites pos-
sess synergistic theranostic effects on in vivo applications. Liu
et al. proposed a type of pH-responsive nanoplatform denoted 5.3. Other Biological Applications of LCOFs
as MnO2/ZnCOF@Au&bovine serum albumin (BSA), where
BSA was short for bovine serum albumin, for applications in The porous structure and photoluminescent property of LCOFs
cancer diagnostics and therapy.[46] They synthesized ZnCOF inherently favor the application for in vivo drug delivery. Wang
utilizing zinc-meso-tetra(4-aminophenyl) porphyrin (Zn-TAPP) et al. utilized preconjugated monomers, tri(4-formylphenyl)
fluorescent dyes and glyoxal through a Schiff base reaction amines (TPA-CHO) and benzidine to synthesize the LCOF via
with MnO2 nanosheets as a template. Then AuNPs were in situ solvothermal method.[37] The LCOF was then highly loaded
reduced and stabilized in the presence of BSA, which were pre- with doxorubicin (DOX), a fluorescent broad-spectrum anti-
viously absorbed on the surface of MnO2/ZnCOF nanosheets. cancer drug. Additionally, the LCOF and DOX could form a
Figure 13. A) The fluorescence imaging and B) tumor photothermal therapy in vivo. Adapted with permission.[46] Copyright 2019, The Royal Society
of Chemistry.
fluorescence resonance energy transfer system due to their π–π 6. Conclusions and Prospects
and hydrogen bond interactions. Thus, this nanocarrier could
realize the effectively and visually drug loading by simply moni- In summary, this review proposes a classified discussion on
toring color changes of solution with the naked eyes. As shown the current chemical linkages and synthesis methods for the
in Figure 14, it could be clearly seen that the fluorescence building of LCOFs. The combinations of luminescent building
color of the COF solutions gradually changed from light blue blocks are visualized using nine charts divided according to
to orange-red upon the addition of DOX. While under natural the varied linkages. The linking reactions mainly involve the
light, the color was change from light brown to bright yellow and dehydration of boronic acids, the condensation of boronic esters,
to brown red. When the solution pH value increased to 5.0, the and the Schiff base reaction of aldehydes and amines. The pho-
amino groups of DOX were protonated and thus disrupted the tophysical properties of LCOFs have a close relationship with
formation of hydrogen bond, resulting in the release of DOX. their building blocks and structural interactions. The strategies
Therefore, the system could realize pH-responsive drug release of brightening LCOFs are addressed through monomer selec-
under tumor acidic conditions with an excellent anti-migration tion and inter/intramolecular interaction regulation, as well
performance, yielding benign cancer therapeutic effect. as comparative learning from similar luminescent porous
Figure 14. A) The scheme of COF synthesis, visual drug loading, pH-responsive release and cancer therapy. B,a) The fluorescence and b) UV spectra
of DOX with various concentrations of COF. The images of COF solution loaded with different amounts of DOX under c) UV lamp and d) natural light.
Adapted with permission.[37] Copyright 2020, The Royal Society of Chemistry.
materials. The optical properties of LCOFs, combined with and LCOFs with various and distinctive morphologies such
their intrinsic properties as porous polymers, are designed and as nanosheets, nanoflowers and nanobars can be acquired,
used for biorelated applications. Recent advances of LCOFs which will bring the development of LCOFs into the scope of
in biosensing mainly focus on the detection of various metal nanoscience.
ions and drugs. A tendency is emerging using LCOFs to detect
biomolecules. The nanosized LCOFs have advantages of phys-
icochemical stability and biocompatibility and can be competi- 6.3. Optical Properties
tive candidates as probes for cell imaging and in vivo imaging.
Although plausible properties and applications of LCOFs, the Currently, the quantum yield of LCOFs is lower than that of
development of LCOFs is still on their early stage. Both the quantum dots or organic dyes, although many efforts have
library of LCOFs and the biological potentials need to be broad- been undertaken to improve their luminescence quantum
ened and developed, respectively. Challenges and prospects yield. The introduction of novel AIEgens seems to be one of
from the aspects of synthesis, structure, properties and applica- most efficient routes to eliminate of common ACQ effect and
tions are encountered in the development of LCOFs. brighten LCOFs. Additionally, structure modeling of existing
LCOFs can theoretically understand photoluminescent prop-
erties, such as absorption bands, energy band gap, and charge
6.1. Synthetic Methodology transfer. Structure adjustment via computational simulations
should be a powerful tool for optimization of LCOFs with
So far, the LCOFs have been mainly synthesized under harsh improved luminescent properties. As the database of LCOFs
solvothermal conditions, such as high reaction temperature, is enriched, molecule design on the basis of machine learning
long reaction time and complex reaction processes. How- should be a useful method to help us to continuously dig up
ever, only a few methods have been reported to fast and new LCOFs with desired photophysical properties.
readily synthesize LCOFs. More facile and green methods are
urged to lowering the complication and cost of LCOF prepa-
rations. On the other hand, several challenges lie in linkage 6.4. Biorelated Applications
technologies and novel building blocks. For example, the
boron-containing LCOFs are probably not suitable for biore- At present, the analytical applications of LCOFs are mainly
lated applications because the boronic esters and boroxines focused on the detection of explosives and metal ions. The
are very easy to hydrolyze, while the imine bonds show sig- biorelated applications of LCOFs such as biomacromolecule
nificantly higher stability and benign pH response than the sensing and drug delivery, are far from enough. Few reports
boronic esters. When design LCOFs for the applications of can be found on sensitive detection of RNA, proteins, or poly-
bioimaging or drug delivery, building blocks with imine pre- saccharide. It is still in the infancy stage of LCOFs in the field of
cursor groups are suggested. Future efforts on LCOF chem- biomedical application. Future efforts can be dedicated to modi-
istry could be directed to methodologies and techniques of fication of LCOFs with functional groups to enhance specific
facile and green preparation of LCOFs. Several aspects could molecule recognition, synthesis of LCOFs with near-infrared
be considered, such as simplification of synthetic processes, emission properties to realize bioimaging with low background
standardization of solvent usage and introduction/develop- and high sensitivity, combination the pH response of LCOFs
ment of suitable chemical technologies. Mostly importantly, with pore selectivity to achieve drug delivery in specific tissues,
the choices or innovations of chemical linkages and building and exploration of novel sensing mechanisms about detec-
blocks are expected to be more sophisticated and under tion of biomacromolecules such as proteins and nucleic acids.
rational design with the help of modern computational simu- Notably, the toxicity and metabolic kinetics of LCOFs should be
lation technology. further studied for in vivo applications. The future development
of LCOFs in biorelated applications is expected to be carried out
through multidisciplinary collaborations from fields, such as
6.2. Structures chemistry, physics, materials science, computing science, and
biology.
LCOFs have their unique advantages such as tunability
of luminescent building blocks and topological structure
through rationally designed synthetic chemistry in compar- Acknowledgements
ison with other luminescent porous materials. A fair number
of researches have showed that multidimensional and multi- The authors acknowledge funding from the National Natural Science
morphological structures of LCOFs might generate intriguing Foundation of China (21904011, 21890742, and 21727815). This work
was also supported by the Open Fund of Guangdong Provincial Key
photoelectrical effects and exotic biological properties. For Laboratory of Luminescence from Molecular Aggregates, Guangzhou
example, 3D nano-LCOFs are expected to possess higher sur- 510640, China (South China University of Technology) (2019B030301003).
face area, lower density and more open functional sites, while
the current LCOFs are 2D structures mostly. In the future, the
building blocks with nonplanar structure should be designed
and used to construct LCOFs with 3D network structure. In Conflict of Interest
additionally, nanotechnologies of LCOFs should be developed The authors declare no conflict of interest.
Keywords [26] K. Wang, W. Wang, S. Pan, Y. Fu, B. Dong, H. Wang, Appl. Mater.
Today 2020, 19, 100550.
bioimaging, biosensing, building block linkages, luminescent covalent [27] M.-W. Zhu, S.-Q. Xu, X.-Z. Wang, Y. Chen, L. Dai, X. Zhao, Chem.
organic frameworks, photoluminescence Commun. 2018, 54, 2308.
[28] Q. Gao, X. Li, G.-H. Ning, K. Leng, B. Tian, C. Liu, W. Tang,
Received: June 16, 2021 H.-S. Xu, K. P. Loh, Chem. Commun. 2018, 54, 2349.
Revised: August 16, 2021 [29] C. Zhang, S. Zhang, Y. Yan, F. Xia, A. Huang, Y. Xian, ACS Appl.
Published online: October 3, 2021 Mater. Interfaces 2017, 9, 13415.
[30] X. Wang, C. Zhang, Y. Zhao, S. Ren, J.-X. Jiang, Macromol. Rapid
Commun. 2016, 37, 323.
[31] M. Faheem, S. Aziz, X. Jing, T. Ma, J. Du, F. Sun, Y. Tian, G. Zhu, J.
[1] W. K. Haug, E. M. Moscarello, E. R. Wolfson, P. L. McGrier, Chem. Mater. Chem. A 2019, 7, 27148.
Soc. Rev. 2020, 49, 839. [32] P. Albacete, A. Lopez-Moreno, S. Mena-Hernando, A. E. Platero-Prats,
[2] X. Chen, K. Geng, R. Liu, K. T. Tan, Y. Gong, Z. Li, S. Tao, Q. Jiang, E. M. Perez, F. Zamora, Chem. Commun. 2019, 55, 1382.
D. Jiang, Angew. Chem., Int. Ed. 2020, 59, 5050. [33] S. Liu, C. Hu, Y. Liu, X. Zhao, M. Pang, J. Lin, Chem. - Eur. J. 2019,
[3] J.-Y. Zeng, X.-S. Wang, X.-Z. Zhang, Chem. - Eur. J. 2020, 26, 16568. 25, 4315.
[4] R. Xue, H. Guo, T. Wang, L. Gong, Y. Wang, J. Ai, D. Huang, [34] D. Wang, Z. Zhang, L. Lin, F. Liu, Y. Wang, Z. Guo, Y. Li, H. Tian,
H. Chen, W. Yang, Anal. Methods 2017, 9, 3737. X. Chen, Biomaterials 2019, 223, 119459.
[5] M. S. Lohse, T. Bein, Adv. Funct. Mater. 2018, 28, 1705553. [35] G. Zhang, X. Li, Q. Liao, Y. Liu, K. Xi, W. Huang, X. Jia, Nat.
[6] S. Wan, J. Guo, J. Kim, H. Ihee, D. Jiang, Angew. Chem., Int. Ed. Commun. 2018, 9, 2785.
2008, 47, 8826. [36] J. Wang, B. Yan, Anal. Chem. 2019, 91, 13183.
[7] G. Lin, H. Ding, D. Yuan, B. Wang, C. Wang, J. Am. Chem. Soc. [37] B. Wang, X. Liu, P. Gong, X. Ge, Z. Liu, J. You, Chem. Commun.
2016, 138, 3302. 2020, 56, 519.
[8] N. Huang, X. Ding, J. Kim, H. Ihee, D. Jiang, Angew. Chem. 2015, [38] F. Zhao, H. Liu, S. D. R. Mathe, A. Dong, J. Zhang, Nanomaterials
54, 8704. 2018, 8, 15.
[9] S. Haldar, D. Chakraborty, B. Roy, G. Banappanavar, K. Rinku, [39] P. Wang, F. Zhou, C. Zhang, S.-Y. Yin, L. Teng, L. Chen, X.-X. Hu,
D. Mullangi, P. Hazra, D. Kabra, R. Vaidhyanathan, J. Am. Chem. H.-W. Liu, X. Yin, X.-B. Zhang, Chem. Sci. 2018, 9, 8402.
Soc. 2018, 140, 13367. [40] E. L. Spitler, B. T. Koo, J. L. Novotney, J. W. Colson, F. J. Uribe-Romo,
[10] H. Wang, Z. Zeng, P. Xu, L. Li, G. Zeng, R. Xiao, Z. Tang, G. D. Gutierrez, P. Clancy, W. R. Dichtel, J. Am. Chem. Soc. 2011,
D. Huang, L. Tang, C. Lai, D. Jiang, Y. Liu, H. Yi, L. Qin, S. Ye, 133, 19416.
X. Ren, W. Tang, Chem. Soc. Rev. 2019, 48, 488. [41] Z. Li, N. Huang, K. H. Lee, Y. Feng, S. Tao, Q. Jiang, Y. Nagao,
[11] Y. Zhao, W. Dai, Y. Peng, Z. Niu, Q. Sun, C. Shan, H. Yang, S. Irle, D. Jiang, J. Am. Chem. Soc. 2018, 140, 12374.
G. Verma, L. Wojtas, D. Yuan, Z. Zhang, H. Dong, X. Zhang, [42] Z. Li, Y. Zhang, H. Xia, Y. Mu, X. Liu, Chem. Commun. 2016, 52,
B. Zhang, Y. Feng, S. Ma, Angew. Chem., Int. Ed. 2020, 59, 6613.
4354. [43] E. Jin, J. Li, K. Geng, Q. Jiang, H. Xu, Q. Xu, D. Jiang, Nat.
[12] B.-Q. Li, S.-Y. Zhang, B. Wang, Z.-J. Xia, C. Tang, Q. Zhang, Energy Commun. 2018, 9, 4143.
Environ. Sci. 2018, 11, 1723. [44] W.-R. Cui, W. Jiang, C.-R. Zhang, R.-P. Liang, J. Liu, J.-D. Qiu, ACS
[13] H. Fan, J. Gu, H. Meng, A. Knebel, J. Caro, Angew. Chem., Int. Ed. Sustainable Chem. Eng. 2019, 8, 445.
2018, 57, 4083. [45] S. Ren, M. J. Bojdys, R. Dawson, A. Laybourn, Y. Z. Khimyak,
[14] P. Pachfule, A. Acharjya, J. r. m. Roeser, T. Langenhahn, D. J. Adams, A. I. Cooper, Adv. Mater. 2012, 24, 2357.
M. Schwarze, R. Schomäcker, A. Thomas, J. Schmidt, J. Am. Chem. [46] Y. Liu, Y. Zhang, X. Li, X. Gao, X. Niu, W. Wang, Q. Wu, Z. Yuan,
Soc. 2018, 140, 1423. Nanoscale 2019, 11, 10429.
[15] S. Lu, Y. Hu, S. Wan, R. McCaffrey, Y. Jin, H. Gu, W. Zhang, J. Am. [47] K. Geng, T. He, R. Liu, S. Dalapati, K. T. Tan, Z. Li, S. Tao, Y. Gong,
Chem. Soc. 2017, 139, 17082. Q. Jiang, D. Jiang, Chem. Rev. 2020, 120, 8814.
[16] Y. Zhang, H. Hu, J. Ju, Q. Yan, V. Arumugam, X. Jing, H. Cai, [48] J. W. Crowe, L. A. Baldwin, P. L. McGrier, J. Am. Chem. Soc. 2016,
Y. Gao, Chin. J. Catal. 2020, 41, 485. 138, 10120.
[17] E. Vitaku, C. N. Gannett, K. L. Carpenter, L. Shen, H. D. Abruña, [49] S. Wang, L. Ma, Q. Wang, P. Shao, D. Ma, S. Yuan, P. Lei, P. Li,
W. R. Dichtel, J. Am. Chem. Soc. 2019, 142, 16. X. Feng, B. Wang, J. Mater. Chem. C 2018, 6, 5369.
[18] A. M. Evans, M. R. Ryder, W. Ji, M. J. Strauss, A. R. Corcos, [50] A. M. Evans, I. Castano, A. Brumberg, L. R. Parent, A. R. Corcos,
E. Vitaku, N. C. Flanders, R. P. Bisbey, W. R. Dichtel, Faraday Dis- R. L. Li, N. C. Flanders, D. J. Gosztola, N. C. Gianneschi,
cuss. 2021, 225, 226. R. D. Schaller, W. R. Dichtel, J. Am. Chem. Soc. 2019, 141,
[19] X. Han, J. Zhang, J. Huang, X. Wu, D. Yuan, Y. Liu, Y. Cui, Nat. 19728.
Commun. 2018, 9, 1294. [51] Y.-F. Xie, S.-Y. Ding, J.-M. Liu, W. Wang, Q.-Y. Zheng, J. Mater.
[20] X. Wu, X. Han, Q. Xu, Y. Liu, C. Yuan, S. Yang, Y. Liu, J. Jiang, Chem. C 2015, 3, 10066.
Y. Cui, J. Am. Chem. Soc. 2019, 141, 7081. [52] H.-L. Qian, C. Dai, C.-X. Yang, X.-P. Yan, ACS Appl. Mater. Inter-
[21] P. Das, S. K. Mandal, J. Mater. Chem. A 2018, 6, 16246. faces 2017, 9, 24999.
[22] A. Bhunia, D. Esquivel, S. Dey, R. Fernández-Terán, Y. Goto, S. Inagaki, [53] L. Chen, L. He, F. Ma, W. Liu, Y. Wang, M. A. Silver, L. Chen,
P. Van Der Voort, C. Janiak, J. Mater. Chem. A 2016, 4, 13450. L. Zhu, D. Gui, J. Diwu, Z. Chai, S. Wang, ACS Appl. Mater. Inter-
[23] H. Ding, J. Li, G. Xie, G. Lin, R. Chen, Z. Peng, C. Yang, B. Wang, faces 2018, 10, 15364.
J. Sun, C. Wang, Nat. Commun. 2018, 9, 5234. [54] S. Kandambeth, A. Mallick, B. Lukose, M. V. Mane, T. Heine,
[24] X. Li, Q. Gao, J. Wang, Y. Chen, Z.-H. Chen, H.-S. Xu, W. Tang, R. Banerjee, J. Am. Chem. Soc. 2012, 134, 19524.
K. Leng, G.-H. Ning, J. Wu, Q.-H. Xu, S. Y. Quek, Y. Lu, K. P. Loh, [55] D. Kaleeswaran, P. Vishnoi, R. Murugavel, J. Mater. Chem. C 2015,
Nat. Commun. 2018, 9, 2335. 3, 7159.
[25] S. Wan, J. Guo, J. Kim, H. Ihee, D. Jiang, Angew. Chem., Int. Ed. [56] W.-R. Cui, C.-R. Zhang, W. Jiang, R.-P. Liang, J.-D. Qiu, ACS Appl.
2009, 48, 5439. Nano Mater. 2019, 2, 5342.
[57] W. Liu, Y. Cao, W. Wang, D. Gong, T. Cao, J. Qian, K. Iqbal, W. Qin, [95] Y. Shen, H. Liu, S. Zhang, Y. Gao, B. Li, Y. Yan, Y. Hu, L. Zhao,
H. Guo, Chem. Commun. 2019, 55, 167. B. Yang, J. Mater. Chem. C 2017, 5, 10061.
[58] R. Gomes, A. Bhaumik, RSC Adv. 2016, 6, 28047. [96] S. Chatterjee, H. Gohil, I. Raval, S. Chatterjee, A. R. Paital, Small
[59] Y. Zhang, X. Shen, X. Feng, H. Xia, Y. Mu, X. Liu, Chem. Commun. 2019, 15, 1804749.
2016, 52, 11088. [97] Rohini, M. Baral, B. K. Kanungo, RSC Adv. 2016, 6, 108017.
[60] S.-Y. Ding, M. Dong, Y.-W. Wang, Y.-T. Chen, H.-Z. Wang, C.-Y. Su, [98] F. A. S. Chipem, A. Mishra, G. Krishnamoorthy, Phys. Chem. Chem.
W. Wang, J. Am. Chem. Soc. 2016, 138, 3031. Phys. 2012, 14, 8775.
[61] S. K. Konavarapu, K. Biradha, Cryst. Growth Des. 2018, 19, 362. [99] E. Lippert, W. Lüder, F. Moll, W. Nägele, H. Boos, H. Prigge,
[62] T. Geng, M. Liu, C. Zhang, C. Hu, H. Y. Xia, Polym. Adv. Technol. I. Seibold-Blankenstein, Angew. Chem. 1961, 73, 695.
2020, 31, 1388. [100] L.-L. Wang, C.-X. Yang, X.-P. Yan, Sci. China: Chem. 2018, 61, 1470.
[63] T. Wang, R. Xue, H. Chen, P. Shi, X. Lei, Y. Wei, H. Guo, W. Yang, [101] C.-R. Zhang, W.-R. Cui, W. Jiang, F.-F. Li, Y.-D. Wu, R.-P. Liang,
New. J. Chem. 2017, 41, 14272. J.-D. Qiu, Environ. Sci.: Nano 2020, 7, 842.
[64] E. Özdemir, D. Thirion, C. T. Yavuz, RSC Adv. 2015, 5, 69010. [102] F.-F. Li, W.-R. Cui, W. Jiang, C.-R. Zhang, R.-P. Liang, J.-D. Qiu, J.
[65] Y. He, X. Wang, K. Wang, L. Wang, Dyes Pigm. 2020, 173, 107880. Hazard. Mater. 2020, 392, 122333.
[66] P. Wen, C. Zhang, Z. Yang, R. Dong, D. Wang, M. Fan, J. Wang, [103] W.-R. Cui, C.-R. Zhang, W. Jiang, F.-F. Li, R.-P. Liang, J. Liu,
Tribol. Int. 2017, 111, 57. J.-D. Qiu, Nat. Commun. 2020, 11, 436.
[67] M. Li, Z. Cui, S. Pang, L. Meng, D. Ma, Y. Li, Z. Shi, S. Feng, [104] G. Das, B. P. Biswal, S. Kandambeth, V. Venkatesh, G. Kaur,
J. Mater. Chem. C 2019, 7, 11919. M. Addicoat, T. Heine, S. Verma, R. Banerjee, Chem. Sci. 2015, 6,
[68] H. Li, A. D. Chavez, H. Li, H. Li, W. R. Dichtel, J.-L. Bredas, J. Am. 3931.
Chem. Soc. 2017, 139, 16310. [105] A. Mal, R. K. Mishra, V. K. Praveen, M. A. Khayum, R. Banerjee,
[69] W. Zhang, L.-G. Qiu, Y.-P. Yuan, A.-J. Xie, Y.-H. Shen, J.-F. Zhu, A. Ajayaghosh, Angew. Chem., Int. Ed. 2018, 57, 8443.
J. Hazard. Mater. 2012, 221, 147. [106] P. Albacete, J. I. Martinez, X. Li, A. Lopez-Moreno, S. Mena-
[70] M. Zhang, Y. Li, L. Ma, X. Guo, X. Li, K. Li, X. Wang, C. Xia, S. Li, Hernando, A. E. Platero-Prats, C. Montoro, K. P. Loh, E. M. Perez,
Chem. Commun. 2020, 56, 880. F. Zamora, J. Am. Chem. Soc. 2018, 140, 12922.
[71] M. Sarma, K.-T. Wong, ACS Appl. Mater. Interfaces 2018, 10, 19279. [107] S. Dalapati, C. Gu, D. Jiang, Small 2016, 12, 6513.
[72] J. Wang, F. Lv, L. Liu, Y. Ma, S. Wang, Coord. Chem. Rev. 2018, 354, [108] J. Wu, W. Liu, J. Ge, H. Zhang, P. Wang, Chem. Soc. Rev. 2011, 40,
135. 3483.
[73] T. R. Pavase, H. Lin, S. Hussain, Z. Li, I. Ahmed, L. Lv, L. Sun, [109] A. C. Sedgwick, L. Wu, H.-H. Han, S. D. Bull, X.-P. He, T. D. James,
S. B. H. Shah, M. T. Kalhoro, Sens. Actuators, B 2018, 273, 1113. J. L. Sessler, B. Z. Tang, H. Tian, J. Yoon, Chem. Soc. Rev. 2018, 47,
[74] Y. Zhang, D. Zhang, H. Liu, Polymers 2019, 11, 708. 8842.
[75] C. E. Wayne, R. P. Wayne, Photochemistry, Oxford University Press, [110] J. Perego, J. Pedrini, C. X. Bezuidenhout, P. E. Sozzani, F. Meinardi,
1996. S. Bracco, A. Comotti, A. Monguzzi, Adv. Mater. 2019, 31,
[76] Y. Yamaguchi, Y. Matsubara, T. Ochi, T. Wakamiya, Z.-i. Yoshida, 1903309.
J. Am. Chem. Soc. 2008, 130, 13867. [111] J. Perego, I. Villa, A. Pedrini, E. Padovani, R. Crapanzano,
[77] Y. Li, Y. Han, M. Chen, Y. Feng, B. Zhang, RSC Adv. 2019, 9, 30937. A. Vedda, C. Dujardin, C. X. Bezuidenhout, S. Bracco, P. Sozzani,
[78] H.-Q. Yin, F. Yin, X.-B. Yin, Chem. Sci. 2019, 10, 11103. Nat. Photonics 2021, 15, 393.
[79] Y. Hong, J. W. Y. Lam, B. Z. Tang, Chem. Soc. Rev. 2011, 40, 5361. [112] Y. Zhang, S. Yuan, G. Day, X. Wang, X. Yang, H.-C. Zhou, Coord.
[80] J. Mei, Y. Hong, J. W. Y. Lam, A. Qin, Y. Tang, B. Z. Tang, Adv. Chem. Rev. 2018, 354, 28.
Mater. 2014, 26, 5429. [113] Y. Luo, S. Fan, W. Yu, Z. Wu, D. A. Cullen, C. Liang, J. Shi, C. Su,
[81] J. Mei, N. L. C. Leung, R. T. K. Kwok, J. W. Y. Lam, B. Z. Tang, Adv. Mater. 2018, 30, 1704576.
Chem. Rev. 2015, 115, 11718. [114] E. Priyadarshini, N. Pradhan, Sens. Actuators, B 2017, 238, 888.
[82] L. Ma, X. Feng, S. Wang, B. Wang, Mater. Chem. Front. 2017, 1, [115] B. Kaur, N. Kaur, S. Kumar, Coord. Chem. Rev. 2018, 358, 13.
2474. [116] X. Wu, Q. Huang, Y. Mao, X. Wang, Y. Wang, Q. Hu, H. Wang,
[83] S. Dalapati, E. Jin, M. Addicoat, T. Heine, D. Jiang, J. Am. Chem. X. Wang, TrAC, Trends Anal. Chem. 2019, 118, 89.
Soc. 2016, 138, 5797. [117] K. Wechakorn, S. Prabpai, K. Suksen, P. Piyachaturawat,
[84] J. Dong, X. Li, S. B. Peh, Y. D. Yuan, Y. Wang, D. Ji, S. Peng, G. Liu, P. Kongsaeree, RSC Adv. 2016, 6, 24752.
S. Ying, D. Yuan, J. Jiang, S. Ramakrishna, D. Zhao, Chem. Mater. [118] H. Zhang, Y. Chen, M. Liang, L. Xu, S. Qi, H. Chen, X. Chen, Anal.
2018, 31, 146. Chem. 2014, 86, 9846.
[85] K.-Y. Lai, T.-M. Chu, F. C.-N. Hong, A. Elangovan, K.-M. Kao, [119] S. Liu, R. Liu, X. Xing, C. Yang, Y. Xu, D. Wu, RSC Adv. 2016, 6,
S.-W. Yang, T.-I. Ho, Surf. Coat. Technol. 2006, 200, 3283. 31884.
[86] K. Prasad, R. Haldar, T. K. Maji, RSC Adv. 2015, 5, 74986. [120] X. Wu, Q. Niu, T. Li, Sens. Actuators, B 2016, 222, 714.
[87] I. O. Aparin, G. V. Proskurin, A. V. Golovin, A. V. Ustinov, [121] G. Chen, H.-H. Lan, S.-L. Cai, B. Sun, X.-L. Li, Z.-H. He,
A. A. Formanovsky, T. S. Zatsepin, V. A. Korshun, J. Org. Chem. S.-R. Zheng, J. Fan, Y. Liu, W.-G. Zhang, ACS Appl. Mater. Interfaces
2017, 82, 10015. 2019, 11, 12830.
[88] J. Duhamel, Langmuir 2012, 28, 6527. [122] A. Panda, Y. Yang, S. Venkateswarlu, Y. Son, T.-H. Bae, M. Yoon,
[89] D. Sahoo, V. Narayanaswami, C. M. Kay, R. O. Ryan, Biochemistry Microporous Mesoporous Mater. 2020, 306, 110399.
2000, 39, 6594. [123] E. M. Nolan, S. J. Lippard, Chem. Rev. 2008, 108, 3443.
[90] F. M. Winnik, Chem. Rev. 1993, 93, 587. [124] D. T. Quang, J. S. Kim, Chem. Rev. 2010, 110, 6280.
[91] P. Conlon, C. J. Yang, Y. Wu, Y. Chen, K. Martinez, Y. Kim, [125] P. R. Sharma, A. Chattopadhyay, S. K. Sharma, B. S. Hsiao, Ind.
N. Stevens, A. A. Marti, S. Jockusch, N. J. Turro, W. Tan, J. Am. Eng. Chem. Res. 2017, 56, 13885.
Chem. Soc. 2008, 130, 336. [126] H. Xu, M. Fang, C.-S. Cao, W.-Z. Qiao, B. Zhao, Inorg. Chem. 2016,
[92] S. Dalapati, S. Jin, J. Gao, Y. Xu, A. Nagai, D. Jiang, J. Am. Chem. 55, 4790.
Soc. 2013, 135, 17310. [127] S. L. Yao, X. M. Tian, L. Q. Li, S. J. Liu, T. F. Zheng, Y. Q. Chen,
[93] P. F. Jones, M. Nicol, J. Chem. Phys. 1965, 43, 3759. D. S. Zhang, J. L. Chen, H. R. Wen, T. L. Hu, Chem. Asian J. 2019,
[94] J. K. McVey, D. M. Shold, N. C. Yang, J. Chem. Phys. 1976, 65, 3375. 14, 3648.
[128] Y. Chen, T. Wei, Z. Zhang, T. Chen, J. Li, J. Qiang, J. Lv, F. Wang, [141] K. G. Lloyd, L. Davidson, O. Hornykiewicz, J. Pharmacol. Exp. Ther.
X. Chen, Ind. Eng. Chem. Res. 2017, 56, 12267. 1975, 195, 453.
[129] N. Ding, D. Zhou, G. Pan, W. Xu, X. Chen, D. Li, X. Zhang, J. Zhu, [142] J. Dong, X. Li, K. Zhang, Y. D. Yuan, Y. Wang, L. Zhai, G. Liu,
Y. Ji, H. Song, ACS Sustainable Chem. Eng. 2019, 7, 8397. D. Yuan, J. Jiang, D. Zhao, J. Am. Chem. Soc. 2018, 140, 4035.
[130] K. Wechakorn, S. Prabpai, K. Suksen, P. Kanjanasirirat, [143] C. Liu, D. Xie, P. Liu, S. Xie, S. Wang, F. Cheng, M. Zhang, L. Wang,
Y. Pewkliang, S. Borwornpinyo, P. Kongsaeree, Luminescence 2018, Microchim. Acta 2019, 186, 21.
33, 64. [144] L. Han, Y. Zhao, C. Chang, F. Li, J. Electroanal. Chem. 2018, 817, 141.
[131] L. Tang, P. He, K. Zhong, S. Hou, Y. Bian, Spectrochim. Acta, Part [145] J.-M. Wang, X. Lian, B. Yan, Inorg. Chem. 2019, 58, 9956.
A 2016, 169, 246. [146] X. Bai, Y. Huang, M. Lu, D. Yang, Angew. Chem. 2017, 56, 12873.
[132] Y. Cai, Y. Jiang, L. Feng, Y. Hua, H. Liu, C. Fan, M. Yin, S. Li, X. Lv, [147] Z. Du, B. Song, W. Zhang, C. Duan, Y. L. Wang, C. Liu, R. Zhang,
H. Wang, Anal. Chim. Acta 2019, 1057, 88. J. Yuan, Angew. Chem., Int. Ed. 2018, 57, 3999.
[133] C. Cui, Q. Wang, C. Xin, Q. Liu, X. Deng, T. Liu, X. Xu, X. Zhang, [148] Y. L. Pak, J. Li, K. C. Ko, G. Kim, J. Y. Lee, J. Yoon, Anal. Chem.
Microporous Mesoporous Mater. 2020, 299, 110122. 2016, 88, 5476.
[134] J. Liao, Z. Cheng, L. Zhou, ACS Sustainable Chem. Eng. 2016, 4, [149] G. Xu, Q. Yan, X. Lv, Y. Zhu, K. Xin, B. Shi, R. Wang, J. Chen,
3053. W. Gao, P. Shi, C. Fan, C. Zhao, H. Tian, Angew. Chem. 2018, 57,
[135] S. Syed, Hydrometallurgy 2012, 115, 30. 3626.
[136] Z. Liu, M. Frasconi, J. Lei, Z. J. Brown, Z. Zhu, D. Cao, [150] T. Wang, E. F. Douglass Jr, K. J. Fitzgerald, D. A. Spiegel, J. Am.
J. Iehl, G. Liu, A. C. Fahrenbach, Y. Y. Botros, O. K. Farha, Chem. Soc. 2013, 135, 12429.
J. T. Hupp, C. A. Mirkin, J. F. Stoddart, Nat. Commun. 2013, 4, [151] W. Ma, X. Li, Y. Bai, H. Liu, TrAC, Trends Anal. Chem. 2018, 109, 154.
1855. [152] C. Luan, Z. Yang, B. Chen, J. Fluoresc. 2016, 26, 1131.
[137] C. Yue, H. Sun, W.-J. Liu, B. Guan, X. Deng, X. Zhang, P. Yang, [153] G. Das, F. Benyettou, S. K. Sharama, T. Prakasam, F. Gándara,
Angew. Chem. 2017, 56, 9331. V. A. de la Peña-O’Shea, N. i. Saleh, R. Pasricha, R. Jagannathan,
[138] T. H. Nguyen, L. Wang, M. S. Lee, Korean J. Met. Mater. 2017, 55, M. A. Olson, A. Trabolsi, Chem. Sci. 2018, 9, 8382.
247. [154] J.-Y. Zeng, X.-S. Wang, B.-R. Xie, M.-J. Li, X.-Z. Zhang, Angew.
[139] Z. Zhou, W. Zhong, K. Cui, Z. Zhuang, L. Li, L. Li, J. Bi, Y. Yu, Chem. 2019, 132, 10173.
Chem. Commun. 2018, 54, 9977. [155] Y. Zhang, C. Zhang, C. Xu, X. Wang, C. Liu, G. I. N. Waterhouse,
[140] M. A. T. Blaskovich, J. Med. Chem. 2016, 59, 10807. Y. Wang, H. Yin, Talanta 2019, 200, 432.
Jianxin Ma received her Bachelor of Science in June 2020 from University of Science and
Technology Beijing, China. She is currently a Ph.D. candidate under Prof. Xueji Zhang at the
School of Biomedical Engineering, Health Science Center, Shenzhen University. Her main
research content is the self-assembly based on COFs and MOFs of gold nanoclusters.
Tong Shu is an assistant professor at Shenzhen University, China. He received his B.S. in 2010
and Ph.D. in 2015 in biotechnology and analytical chemistry, respectively, from the University of
Science and Technology Beijing, China. He completed his post-doctoral studies at the University
of Alberta, Canada from 2016 to 2017. Afterward, he worked in Research Center for Bioengineering
and Sensing Technology, University of Science and Technology Beijing, China as an assistant
professor from 2017 to 2020. In 2020, he joined the School of Biomedical Engineering, Health
Science Center, Shenzhen University, China. His current work involves metal clusters and frame
polymers and their applications in biosensing and biomedicine.
Xueji Zhang is vice president of Shenzhen University and Professor in the School of Biomedical
Engineering, P. R. China. He received his B.Sc. and Ph.D. from Wuhan University in 1989 and
1994, respectively. His research interests span the disciplines of chemistry, biology, materials, and
medicine with an emphasis on studies of biosensing, biomedicine, and biomaterials.

Small - 2021 - Ma - Luminescent Covalent Organic Frameworks For Biosensing and Bioimaging Applications

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Luminescent Covalent Organic Frameworks for Biosensing

and have attracted wide attention because

Small 2022, 18, 2103516 2103516 (1 of 30) © 2021 Wiley-VCH GmbH

2.1.1. Boronic Esters and Boroxines 2.1.2. Imines

Small 2022, 18, 2103516 2103516 (2 of 30) © 2021 Wiley-VCH GmbH

TP-COF HHTP-DPB-COF Not found BZL-COF

Py-DBA-COF 1 Not found Not found Not found

Py-DBA-COF 2 Not found Not found Not found

Not found Not found Ph-An-COF Not found

Scheme 1. The synthesis of boronic ester-linked LCOFs.

Small 2022, 18, 2103516 2103516 (3 of 30) © 2021 Wiley-VCH GmbH

Ph-COF BPh-COF DBD-COF PPy-COF

Scheme 2. The synthesis of boroxine-linked LCOFs through self-condensation.

Small 2022, 18, 2103516 2103516 (4 of 30) © 2021 Wiley-VCH GmbH

was attained by condensation of 1,3,6,8-tetrakis(4-formylphenyl) 2.1.5. Imides

Small 2022, 18, 2103516 2103516 (5 of 30) © 2021 Wiley-VCH GmbH

© 2021 Wiley-VCH GmbH

Small 2022, 18, 2103516

© 2021 Wiley-VCH GmbH

Small 2022, 18, 2103516

Small 2022, 18, 2103516 2103516 (8 of 30) © 2021 Wiley-VCH GmbH

Small 2022, 18, 2103516 2103516 (9 of 30) © 2021 Wiley-VCH GmbH

Scheme 4. The synthesis of ketoenamine-linked LCOFs.

Not found TFPB-DHzDR TFPPy-DETHz- COF-JLU4

(R=M, Pr, All, S)

Not found COF-LZU8 Not found Not found Not found

Not found TTB-COF Not found Not found Not found

DFDM-THz Not found TFPB-THz Not found Not found

Scheme 5. The synthesis of hydrazone-linked LCOFs.

Py-Azine-COF COF-LJU3 COF-1

Scheme 6. The synthesis of azine-linked LCOFs.

P1/P1M P2/P2M P3/P3M P4/P4M P5/P5M

Scheme 7. The synthesis of luminescent CTFs through self-condensation.

3.2.2. Flexible Building Units

PI-COF-201 PI-COF-202 Not found

Not found Not found

Scheme 8. The synthesis of imide-linked LCOFs.

sp2c-COF Not found Not found

sp2c-COF-2 Not found Not found

Scheme 9. The synthesis of LCOFs through Knoevenagel condensation.

3.2.4. Excimer Molecules and hydroxyquinolines, also have luminescence properties.[93–97]

In order to overcome the thermal decay of excited states induced

of pore microenvironments of COFs to allow precursors to 4.1.2. Hg2+ Sensors

4.1.6. Au3+ Sensors

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