COF Catalysis

Title: Covalent Organic Frameworks in Catalytic Organic Synthesis
Authors: Haiyang Cheng and Tao Wang
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Advanced Synthesis & Catalysis 10.1002/adsc.202001086
REVIEW
DOI: 10.1002/adsc.202001086
Covalent Organic Frameworks in Catalytic Organic Synthesis

Hai-Yang Cheng a and Tao Wang *a
a
Key Laboratory of Applied Surface and Colloid Chemistry, Ministry of Education, School of Chemistry and Chemical
Engineering, Shaanxi Normal University, Xi’an 710119, China
Email: 459316706@qq.com (Hai-Yang Cheng), chemtao@snnu.edu.cn (Tao Wang).
Received: ((will be filled in by the editorial staff))
Abstract. Covalent organic frameworks (COFs), which are catalysis of organic reactions. As heterogeneous organic
Accepted Manuscript
built upon dynamic covalent chemistry (DCC) with various catalysts, COFs bring benefits and solve problems, but also
organic building blocks, possess predesignable, highly create new obstacles. Hence, we would like to establish a
ordered and crystalline porous structures. These features comprehensive system to review some pioneering works in
endow COFs with great potential in the development of this area. This will help us get a better view so that we can
function-tailored materials, particularly in catalytic organic discuss the key and challenging issues we are currently
synthesis. Start from selective oxidation reactions early confronted with.
introduced by Ferdi, Thomas and their co-workers, and then
Wang and co-workers performed Suzuki-Miyaura reaction Keywords: Covalent organic frameworks; Organic
through integrating palladium into COFs, increasing numbers Synthesis; Catalysis
of works were established to explore their potentials in the
1 Introduction equilibrium was built upon dynamic covalent

chemistry. [5] This allows the activation of self-healing
High catalytic activity, extraordinary chemo-/stereo- in certain synthetic conditions; (3) highly-ordered
/enantio-selectivity, robust stability, eco-friendly and structures, benefiting from the self-healing ability and
cost-efficient are always the pursues in catalysis, not rigidity of backbones, COFs possess long-ranged-
only for lab experiments, but also for industrial ordered structures and excellent crystallinity.
productions. Heterogeneous catalysts are optimal
choices to deal with the cost and environmental issues
owing to their recyclability. For example, zeolites are Hai-Yang Cheng, a graduate
great industrial catalysts for petroleum processing in student of Shaanxi Norma
early stage.[1] After that, the catalytic performance of University, obtained his bachelor
degree in 2020. He joined Wang’s
other potential heterogenous catalysts, such as metal group in 2018 and worked on
organic frameworks (MOFs)[2] and porous organic gold-catalyzed reactions and
polymers (POPs)[3], were also evaluated. Great functional organic materials.
improvements have been achieved in the development
of heterogeneous catalysts in the last decades.
However, considering the continuous requirement
from organic synthesis, especially industrial scale ones, Tao Wang received his bachelor’s
catalysts with high activity and selectivity are still degree from Zhengzhou University
highly desired. in 2007, and his master’s degree
Covalent organic frameworks (COFs) are usually from East China Normal
comprised of organic building knots and reversible University under the direction of
covalent linkages.[4] The word “framework” is a Professor Junliang Zhang in 2011.
precise description for COFs considering their highly At the same year, he joined the
group of A. S. K. Hashmi in
ordered structures, just like toy bricks (Scheme 1) we Heidelberg, Germany. In 2014 he
played with as kids. COFs possess following traits: (1) completed his PhD degree and
the high expansibility endowed by the diversity of started his independent research
organic building blocks and the variety of potential at Shaanxi Normal University. His current research
applications; (2) self-healing ability, the formation of interests focus on the development of gold-catalyzed
reversible bonds controlled by thermodynamic reactions and metal-free transformations.
This article is protected by copyright. All rights reserved.

Accepted Manuscript
Scheme 1. Pioneering works of COFs in catalytic organic synthesis.
the embryos of diverse n-type, p-type and ambipolar-

type semiconductors;[11-12] the incorporation of organic
precursors with special photoelectron properties, such
as phthalocyanine and pyrene, made COFs as
luminescence and sensors;[13-14] the well-ordered 1D
channels ranged in COFs help substrates/products
transport, which simulates similar environment in
homogenous catalysis, making COFs great candidates
in industrial catalysis.[15] Apart from these, COFs were
also applied in lithium battery[16-17], proton transport[18-
19]
, chiral separation[20-21] etc.
Many efforts have been devoted to the exploration
Fig 1. Growth trend of numbers of papers on COFs in of COFs in catalytic organic synthesis in the last
catalytic organic synthesis. decade. Considering the inherent advantages of COFs
for heterogeneous catalysis, considerable pioneering
works were accomplished to serve as the corner stones
Both MOFs and COFs are designed according to in this field (Scheme 1). For example, the year 2005
reticular chemistry[6-7], therefore, MOFs supply ample was marked by the synthesis of COF1/5,[22] and the
examples with chemists to explore and develop COFs. first catalytic example in organic synthesis was
Considering the diversity of organic precursors, the explored by Ferdi and co-workers in 2009: a selective
function-tailored COFs were designed into various oxidation reaction catalyzed by metal-based CTF
practical and productive material. For instance, the (covalent triazine frameworks)[23] (a).[24] In 2011,
adsorption capacity for gas storage of porous materials Wang and co-workers reported a Pd/COF-LZU1
was a standard index for their applications, which catalyzed Suzuki coupling reaction,[15] which drew
indicates their surface area and porosity;[8-10] the chemists’ attention to COFs in catalytic organic
integration of conjugated π-units into the backbones of synthesis. After that, various organic reactions
COFs enables them to form ordered columnar π-arrays, catalyzed by COFs were developed (Fig 1). Such as
CO2 reductive reaction (c) developed by Thomas et

al.,[25] asymmetric Michael addition reaction (e),[26] chemoselectivity. Apart from that, no significant loss
Diels-Alder reaction (f)[27] exploited by Jiang’s group, of activity was observed within three recycles.
and the kinetic resolution of alcohols (i) catalysed by However, TFP-DABA lost its crystallinity due to
enzymes-infiltrated COFs,[28] organic reactions partial exfoliation, which was further confirmed by
catalyzed by COFs exhibited superior performance FTIR spectrum and PXRD patterns.
when compared to their homogeneous counterparts.
As COFs attract more and more attention, there
have been outstanding reviews carefully illustrated the
general introduction in design principles, structural
diversity and analysis, and synthetic methods of
COFs.[29-30] Moreover, the catalytic application in
oxygen/hydrogen evolution reactions, pollutant
degradation reactions, biochemistry reactions and so
on has also been illustrated.[31-33] However, a Scheme 2. Synthesis of HMF (a) and DFF (b) from fructose
comprehensive review simply for COFs’ catalytic catalyzed by TFP-DABA.
Accepted Manuscript
performance in organic synthesis is still absent.
Therefore, we would like to provide an exhaustive
elaboration of COFs with respect to their functions in There are multiple classes of organic units possess
catalytic organic synthesis in this review. acidity or alkalinity, minute difference may make a
difference. Recently, Long et al. developed two COFs
(TABTA-COF-1/2, Figure 2, Table 1) with benzene-
2. COFs themselves as catalysts in 1,3,5-tricarboxamide (BTA), a building block that
organic synthesis widely utilized for supramolecular assembly owing to
robust intermolecular hydrogen bonding
COFs could play various roles in organic catalysis. In interactions.[35] COFs with amide groups as alkaline
this section, we focus on the ability of COFs active sites are capable of catalyzing the condensation
themselves to catalyze organic reactions. The catalytic reactions inherently. Indeed, both TABTA-COF-1 and
ability of COFs relies on their functional organic TABTA-COF-2 could catalyze the Knoevenagel
precursors. For instance, functional parts with acid or reaction with great yields (up to 99 %). The
alkaline groups like hydroxyl and amino give COFs recyclability was also confirmed by further recycling
the abilities to promote de-protection reactions and tests (Scheme 3, a). Similarly, Zhang and co-workers
condensation reactions. Organic units with special also incorporated a squaramide unit into COFs (COF-
photoelectric properties, such as benzopyrene, are SQ, Figure 2, Table 1) to catalyze Michael addition
incorporated into COFs for their abilities to assist reactions with great yields (up to 98 %) (Scheme 3,
photoelectron-transferring process in visible-light- b).[36] Generally, bifunctional squaramide units
induced reactions. Fundamentally, as porous materials, themselves are great biomimetic organocatalysts,
the adsorption and gas storage ability help COFs to however, their worse reusability is always criticized.
build agreeable environment for gas-participated By incorporating them into COFs, this problem was
reactions, such as CO2 fixation reactions. solved perfectly. Control experiments in both works
revealed that the high catalytic activity belonged to
COFs, instead of their organic precursors. Although
2.1 COFs with acid/alkaline groups in organic the majority of COFs are crystalline powders, Dong
catalysis. and co-workers fabricated nitrogen-doped carbon
nanosheets (NC-700) from self-template COFs (PC-
Base/acid catalysts are widely used in organic COF, Fig 2, Table 1) to enhance its catalytic
transformations including elimination, condensation, activity.[37] Graphitic nitrogen atoms and associated
rearrangement and oxidation reactions. Therefore, defects functionalized as active sites to catalyze
COFs with acidic/basic groups are expected to show Knoevenagel reaction (Scheme 3, d) and
their power in organic reactions as well. hydrogenation of nitroarenes (Scheme 3, c) with
In 2015, Zhao and co-workers reported a stable excellent yields (up to 99 %) and selectivity. It is worth
sulfonated COF (TFP-DABA, Fig 2) to catalyze a noting that metal catalysis (Pd, Au and Pt) are often
biobased chemical conversion: from fructose to 5- involved in hydrogenation of nitroarenes in other
hydroxymethyl-furfural (HMF) and 2,5-diformylfuran reports.
(DFF), respectively (Scheme 2).[34] Irreversible enol-
to-keto tautomerization helped to stabilize the
structure of TFP-DABA. The high stability was
confirmed by thermogravimetric analysis (TGA):
TFP-DABA was thermally stable up to 250 °C (More
data concerning TFP-DABA are displayed in Table 1).
Control experiments and gram-scale reactions were
taken to prove that TFP-DABA was superior to its
homogeneous counterparts in activity and

quickly after several recycles. This result implies the

necessity of improving COFs’ chemical stability.
Scheme 4. Knoevenagel condensation reaction catalyzed
Accepted Manuscript
by BF-COF (a), cascade reaction catalyzed by DL-COF (b)
and 2,3-DhaTph (c).
Scheme 3. Knoevenagel condensation catalyzed by
TABTA-COFs (a), Michael addition reaction catalyzed by
COFs in aforementioned works all functioned as
COF-SQ (b), Hydrogenation of nitrobenzene (c) and
main catalysts in organic synthesis, Li et al. reported a
Knoevenagel condensation(d) catalyzed by NC-700.
highly ordered COFs nanosheets as auxiliary of MOFs
to catalyze the oxidation of styrene (Scheme 5).[41]
NH2-MIL-101(Fe)@NTU-COF, a hybrid material
The function of 3D COFs was confined within gas
with core-shell structure (MOFs@COFs) was
storage in early stage. In 2014, Yan and co-workers
synthesized by coating COFs on top of MOF through
designed and synthesized two 3D COFs (BF-COF-1/2,
the formations of imine group and boroxine ring. The
Figure 2, Table 1) by combining triangular and
COF mainly served as a platform to provide a
tetrahedral building blocks, and then explored their
hydrophobic environment and an agent to promote the
catalytic activity in Knoevenagel condensation
free radical mechanism. Because boroxine ring, a
reaction (Scheme 4, a).[38] Substrates with different
Lewis acid, is beneficial to the electron transfer and
sizes were used in model reactions to testify their size-
catalytic process.
selectivity and that reactions proceeded within COFs
instead of simply on the surface. Simple filtration
helped to reuse the COFs without obvious loss in
activity within three times. Compared with zeolites
and MOFs which were studied for such condensation Scheme 5. The oxidation of styrene catalyzed by NH2-MIL-
reaction, COFs are more stable in structures than those 101(Fe)@NTU-COF.
of MOFs and possess larger pore size and higher
surface area than those of zeolites.
As challengeable as it is, designing and synthesizing Table 1. Relating structure data of TFP-DABA, TABTA-
3D COFs always brings more surprise. Qiu and co- COF-1, TABTA-COF-2, COF-SQ, PC-COF, BF-COF-1,
workers continued to explore and design 3D COFs BF-COF-2, DL-COF-1, DL-COF-2 and 2,3-DhaTph.
(DL-COF-1, DL-COF-2, Fig 2, Table 1) with dual BET Average
linkages (boroxine and imine), which incorporated Pore
TGA Surface Pore
both acid and alkaline as active sites in 2016.[39] This COF volume Ref.
(oC) Area size
enabled COFs to catalyze a cascade reaction as (cm3g-1)
(m2g-1) (nm)
bifunctional catalysts (Scheme 4, b). This work used TFP-
dual linkages to realize different functions in one 250 158.6 1.4 0.48 [34]
DABA
system, which showed us the potential of COFs to TABTA-
finish more than one task at the same time. We are also 410 246 3.68 [35]
COF-1
going to illustrate bimetallic-based COFs to catalyze TABTA-
cascade reaction in following chapter, both 487 368 2.32 [35]
COF-2
demonstrated the benefits brought by the diversity of COF-SQ 380 1195 3.6 [36]
COFs. PC-COF 315 601.4 3.7 [37]
Bifunctional catalysis is not a privilege for 3D COFs, BF-
2D COFs could do the same thing. In 2015, Banerjee 350 730 0.78 0.43 [38]
COF-1
and co-workers designed a 2D COF (2,3-DhaTph, Fig BF-
2, Table 1) with porphyrin and imine as basic sites, 370 680 0.77 0.39 [38]
COF-2
catecholic—OH groups as acidic sites to catalyze a DL-
cascade reaction with excellent activity (96 %) 400 2259 1.36 [39]
COF-1
(Scheme 4, c).[40] Aforementioned COFs all possess DL-
great recyclability. However, the yields dropped 400 2071 1.28 [39]
COF-2

2,3- intermediary agents to help energy transfer from

300 1019 2.2 [40]
DhaTph visible light to substrates, which then turn into radicals
and initiate the reaction. Moreover, there are generally
two quenching cycles for COFs to take part in. The
2.2 Photoelectric properties of COFs in intermediates, however, are different (Fig 3). Wu and
organic catalysis. co-workers reported a hydrazone-based 2D COF
(TFB-COF, Fig 4, Table 2) as recyclable and
Diels–Alder reaction is one of the most effective and productive photocatalyst for cross-dehydrogenative
efficient organic reaction. This reaction generally coupling (CDC) reaction (Scheme 7, a).[43] Similarly,
involves electron transmission between HOMO and Liu’s group also established a 2D COF (COF-JLU5,
LUMO of two substrates and is able to generate four Fig 4, Table 2) to catalyze this reaction (Scheme 7,
chiral centers at most at the same time. The critical part b).[44] Besides, Cui and co-workers illustrated two
in this reaction lies on the electrons transfer process, interpenetrated 3D COFs (COF-1/2 Fig 4, Table 2) to
which decides the rates and the limits of Diels–Alder catalyze the same reaction (Scheme 7, c).[45] Compared
reaction. these works with each other, it is not difficult to find
Accepted Manuscript
that although researchers used various building blocks
to establish diverse COFs, they can catalyze the same
reaction. Because the main point, a suitable electron
transfer station in this reaction, remains unchanged;
the different thing is that Cui and Liu went further to
expand substrate scopes and propose their potential
mechanism of the reaction (Scheme 9, a, b).
Scheme 6. Diels-Alder reaction catalyzed by Py-An COF (a)

and DMTA-TBP1/5' (b).
Jiang and co-workers first introduced COFs (Py-An

COF, Fig 4, Table 2) to catalyze Diels–Alder reaction
under mild conditions (Scheme 6, a).[27] Through
integrating benzopyrene and anthracence, Py-An COF
built up columnar π-walls as catalytic beds together
with well-ordered and open-accessible channels to
facilitate the reaction. The author proposed that the
accumulation of reactants in channels led to enhanced
concentration of substrates, which then intensified the
Scheme 7. CDC reaction catalyzed by TFB-COF (a), COF-
C-H···π interactions between π-walls of COFs and
JLU5 (b), and COF-1/2 (c).
substrates. This interaction was also validated by
previously reported single crystal structure. Once this
C-H···π interactions are strengthened, a decrease of
entropy loss and activation energy helped to speed up
the reaction. And of course, Py-An COF remained
highly active within four recycle tests. Cui and co-
workers also designed a series of chiral COFs
(DMTA-TPBn et al., Fig 6, Table 5) to catalyze
asymmetric Diels-Alder reaction (Scheme 6, b),[42]
which we will elaborate in the following section.
Free radical chemistry received little attentions in
early stage due to their untamed nature, but it is a hot
topic now since many methods were studied to control
free radicals. The high activity of free radicals is a
double-edged sword, which may generate more by-
products, but also make it possible to intrigue reactions Fig 3. Two potential catalytic circles involved in radical
with high energy barrier. Therefore, control them in reaction catalyzed by COFs.
hands may help chemists overcome intractable
obstacles. In this respect, COFs often play as

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Figure 2. Structures of TFP-DABA, TABTA-COF-1, TABTA-COF-2, COF-SQ, PC-COF, BF-COF-1, BF-COF-2, DL-
COF-1, DL-COF-2 and 2,3-DhaTph.

The construction of C-C bond is an indispensable respectively. This further validated their practical
and inevitable task for every organic chemist. Yang and industrial potentials.
co-workers synthesized a hydrazine-based COF (2D-
COF-1, Fig 4, Table 2) to catalyze a tandem radical
addition-cyclization reaction and a direct C3 arylation and
alkylation of quinoxaline-2(1H)-ones under air
environment and visible light condition (Scheme 8).[46-47]
Both of the reactions are traditionally carried out with
radical initiators, transition-metals or organic dyes as
photosensitizers. This work, however, shows us the great
potential for COFs to replace homogeneous metal
catalysts by introducing and tuning functional building
blocks with special photoelectric properties. Given that
both reactions cannot proceed when TEMPO was added
or in the absence of O2, proposed mechanisms were also
put forward (Scheme 9, c, d). It is worth pointing that Scheme 8. C3 arylation (a) and alkylation (b) of quinoxaline-
Accepted Manuscript
gram-scale experiments were carried out in both works 2(1H)-ones catalyzed by 2D-COF-1.
and corresponding yields of 79% and 71% were obtained,
Scheme 9. The potential mechanisms of CDC reaction catalyzed by COF-JLU5 (a) and COF-1/2 (b). The potential mechanisms
of C3 arylation (c) and alkylation of quinoxaline-2(1H)-ones (d) catalyzed by 2D-COF-1.

molecular oxygen rather than water. Plausible

mechanism was then put forward (Scheme 10). Apart
from that, the author found that COFs could also act as
electron donors when iPr2NEt was not added into the
reaction system, but they would lose their activity in
recycling tests. In the end, the author discussed the
correlation between COFs’ structures and activity: (1)
crystalline structures are critical to their high activity
compared to amorphous ones; (2) the benzoxazole
moieties played the major role in photocatalytic activity;
(3) extended π-conjugated frameworks are indispensable
for catalytic activity; (4) COFs themselves could be
electron donors to participate in the photoredox cycle.
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Scheme 10. The oxidation of arylboronic acids to phenols
catalyzed by LZU-190 and its potential mechanism.
The CDC reaction, arylation reaction mentioned above

and the oxidation reactions in the following part all
revolve around molecule O2. The O2 receive energy from Scheme 11. Different visible-light-driven oxidation reaction
light that is transmitted by COFs and then transform into catalyzed by Por-sp2c-COF (a), A2B2-Por-COF (b) and CTF-
superoxide radical anion to initiate the reaction.
Th@SBA-15 (c).
Therefore, how to design COFs with optimal
photocatalytic efficiency is the pivot, and we can learn
from the experience of designing organic
There are other examples of light-driven oxidation
semiconductors: rational electron donor-acceptor (DA) reaction catalyzed by COFs. For example, Wang’s group
structures in the backbone of COFs may help to lower the
reported a 2D porphyrin-based sp2 carbon-conjugated
energetic barrier and delocalize electrons activated by
COF (Por-sp2c-COF, Fig 4, Table 2) to promote visible-
visible light. Apart from that, another crucial problem lies
light-driven aerobic oxidation of amines to imines
with that COFs often use reversible linkages to guarantee
(Scheme 11, a).[49] The utilization of porphyrin building
their high crystallinity. However, this makes COFs much blocks is common in materials relating to the exploitation
vulnerable in photocatalysis due to the energy given by of light energy owing to their special photoelectric
visible light may break up the bonds. Given this situation,
properties. Recently, Chen et al. also took advantage of it
Wang and co-workers established a new method to
and synthesized a porphyrin-based COF (A2B2-Por-COF,
stabilize COFs, which made COFs enduring enough to
Fig 4, Table 2) to oxidize the sulfides under visible light
resist the damage from light. In this method, and oxygen environment (Scheme 11, b).[50] The
benzoxazole-linked COFs (LZU-190, LZU-191, LZU- interesting part is that the synthesis of COF only used a
192, Fig 4, Table 2) were synthesized to catalyze the kind of A2B2 monomer. A2B2-Por-COF could catalyze
oxidation of arylboronic acids to phenols with excellent Knoevenagel condensation due to the alkalinity of
yields (up to 99 %) (Scheme 10).[48] Benzoxazole was
porphyrin units. Another example is a photocatalytic
formed through the cyclization of imine bond and
selective oxidation of benzyl alcohol under oxygen
hydroxyl group with following oxidation. The hydroxyl atmosphere, Zhang et al. developed a CTF (CTF-
group here, worked more like an anchor to strengthen its Th@SBA-15, Fig 4, Table 2) with carefully chosen
stability: the PXRD spectra and 13C CP/MAS NMR of thiophene units to lower the HOMO level and thereby
the COFs remained unchanged even after these COFs
enabling CTF to possess high photooxidation potential to
were immersed by boiling water, pure trifluoroacetic acid,
catalyze this reaction(Scheme 11, c).[51] A plausible
aqueous HCL (9 M) or aqueous NaOH (9 M) for 3 days.
mechanism was also put forward according to control
Intense and continuous exposure to visible light that experiments (Scheme 12, a).
makes normal imine-linked COFs decomposed also Except for superoxide radical anion, there are other
cannot do any harm to their crystalline structures. ESR radicals, all of which play a vital role in organic reactions.
and radical catchers were used to detect the existence of For instance, Liu and co-workers introduced a 2D COF
superoxide radical anion, 18O-labeling experiments
(COF-JLU22, Fig 4, Table 2), which was comprised of
confirmed the oxygen atom in hydroxyl group came from
benzopyrene and thiadiazole units. COF-JLU22 was used

to catalyze visible-light driven dehalogenation reaction and acceptor moieties. The author attributed this
and α-alkylation of aldehydes reaction (Scheme 13, a, b). phenomenon to four divergent molecular D-A domains
[52]
In the dehalogenation reaction, iPr2NEt and Hantzsch in asy-CTF, which led to a broad photogenerated
esters worked as the electron donor and H donor, adsorption range, intramolecular energy transmission
respectively. Plausible mechanisms were proposed and agreeable photoredox potential.
(Scheme 14). Recently, Yang and co-workers also
established a series of COFs (OH-TFP-TTA, OH-TFP-
TAPB et al. Fig 4, Table 2) to catalyze the
dehalogenation reaction and aerobic CDC reaction
(Scheme 13, c, d).[53] In this work, the author found that
the incorporation of hydroxyl group enhanced the
photocatalytic activity by narrowing the band gap of
COFs and thereby promoting charge separation
efficiency and conductivity.
Accepted Manuscript
Scheme 14. Plausible mechanisms of Dehalogenation reaction
(a) and α-alkylation of aldehydes reaction (b) catalyzed by
COF-JLU22.
This speculation was further validated by time-resolved

photoluminescence (TRPL) spectra and control
experiments. Recently, Cai et al. constructed a new
olefin-linked COF (TTO-COF, Fig 4, Table 2) to catalyze
Scheme 12. The plausible mechanisms of oxidation reaction of
the degradation of organic pollutants under visible light
benzyl alcohol (a) and sulphides (b) catalyzed by A2B2-Por-
and the C-H trifluoromethylation of arenes(Scheme 15,
COF (a) and CTF-Th@SBA-15 (b).
b) in the light of Xe lamp. [55] The superoxide radical
anions played different roles in two reactions: they
initiated the degradation after activating by COFs; on the
contrary, CF3 radicals were first activated by COFs to
interact with arenes and the superoxide radical anions
served as terminal oxidant to finish the catalytic circle
(Scheme 16).
Scheme 13. Dehalogenation reaction (a, c), α-alkylation of

aldehydes reaction (b) and CDC reaction (d) catalyzed by
COF-JLU22 and OH-TFP-TTA. Scheme 15. Synthesis of benzophosphole oxides catalyzed by
asy-COF (a) and C-H trifluoromethylation of arenes reaction
catalyzed by TTO-COF (b).
Moreover, Zhang et al. reported an asymmetric CTF
(asy-CTF, Fig 4, Table 2) to catalyze the synthesis of
benzophosphole oxides (Scheme 15, a).[54] The ethoxyl
radical intermediate generated from supplementary
oxidant played the major role in catalytic circle.
Interestingly, the asy-CTF possessed higher light-
induced charge mobility and photocatalytic efficiency
when compared to two symmetric counterparts (CTF-Th,
CTF-Th-Ph, Fig 4, Table 2) that containing akin donor

searching for COFs with excellent stability will always

be a priority for chemists.
Scheme 16. Plausible mechanisms of C-H trifluoromethylation Scheme 18. Macmillan’s work and asymmetric α-alkylation of
of arenes reaction catalyzed by TTO-COF. aldehydes catalyzed by COF-1/2.
As we all know, building chiral centers is always tough
Accepted Manuscript
but critical in organic synthesis, which generally heavily
depends on transition-metals owing to their
comprehensive and systematic studies. Besides, we also
introduced few works that show us the potential for COFs
to substitute transition-metals in visible-light-induced
construction of C-C bonds. In the last section, we would
Scheme 17. Polymerization reaction catalyzed by TTT-DTDA like to introduce an asymmetric α-alkylation of aldehydes
COF (a) and E-Z isomerization reaction catalyzed by TpTt (b). catalyzed by COF-1/2, which were already introduced to
catalyze the CDC reaction.[45] Actually, COFs played the
same role as before, the different thing was that COFs,
Given the high activities of radicals, they are often for the first time, replaced a noble-metal photosensitizer
utilized as initiators of polymerization reactions in early (Ru(bpy)3Cl2) to finish an asymmetric reaction with good
stage. Therefore, Thomas and co-workers learned from yields (up to 88 %) and selectivity (up to 94 %) (Scheme
the design of solar cells and established donor-acceptor 18). Although ruthenium is not expensive when
COFs (TTT-DTDA COF, TTT-BTDA COF, Fig 4, Table compared to other metal photosensitizer like iridium, and
2) to catalyze visible-light-induced free radical the construction of chiral centers still depended on
polymerization with Et3N as co-initiator (Scheme 17, homogeneous co-catalyst (HOTf), this work makes it
a).[56] The COFs here, mainly functioned as the energy possible for COFs to substitute other metals in
absorber and holes generator, which induced hydrogen constructing chiral centers. However, when compared to
abstraction from Et3N to initiate the polymerization of Macmillan’s scaffold, it is easy to find the drawbacks: the
methylmethacrylate (MMA). crystallinity collapsed immediately and needed reprocess
It is easy to find that there is always an agent (O2 or via solvent-assisted linker exchange after reactions,
oxidant additives.) to accept the energy transferred from which set a block for reusability; the overall activity,
COF in aforementioned reactions, this agent turns to chemoselectivity and stereoselectivity still need improve;
radicals to initiate the reaction. The advantage is that it is this reaction was carried out under low temperature and
easy to tailor this agent for receiving energy transferred consecutive visible-light exposure at the same time,
from COFs. Another way is also clear: COFs interact which is unfriendly for the equipment set-up and further
with substrates directly. In 2019, Banerjee and co- amplification.
workers established a 2D COF (TpTt, Fig 4, Table 2) to
catalyze the E-Z isomerization of olefins (Scheme 17,
b).[57] TpTt incorporated triazine core to interact with E
alkenes through strong π-π interactions and β-
ketoenamine unit to strengthen the lifetime of the excited
triplet state of COF. As we have discussed, COF took the
role to absorb energy from visible light and then
transferred them to olefins, this energy turned olefin to a
biradical intermediate state to finish this transformation.
Theoretical calculations were also performed to support
author’s conjectures.
COFs could interact with reactants in multiple ways in
photocatalytic reactions. Although COFs with potential
photocatalytic activity mentioned above possess great
recyclability and reusability, many of them still lost
partial activities after several recycles. Therefore,
10

Scheme 19. Proposed mechanism of asymmetric α-alkylation

of aldehydes catalyzed by COF-1/2.
Accepted Manuscript
11

Accepted Manuscript

Accepted Manuscript
13

Accepted Manuscript
Fig 4. Structures of Py-An COF, 2D-COF-1, COF-JLU5, TFB-COF, COF-1/2, LZU-190/191/192, COF-JLU22, A2B2-Por-COF,
Por-sp2c-COF, OH-TFP-TTA, TTO-COF, TTT-DTDA COF, TTT-BTDA-COF, CTF-Th, CTF-Th-Ph, asy-CTF and TpTt.
Table 2. A summary of structure data of relating COFs mentioned in photoeletric properties of COFs in organic catalysis.
BET Surface Area Average Pore Size Pore Volume Band Gap
COF TGA (oC) Ref.
(m2g-1) (nm) (cm3g-1) (eV)
Py-An COF 400 1479 2.4 0.7 [27]
TFB-COF 375 1501 1.3-2.2 0.88 2.88 [43]
COF-JLU5 450 1632 2.7 1.59 [44]
COF-1 350 624 2.7 2.24 [45]
COF-2 350 570 2.7 2.14 [45]
2D-COF-1 300 2.15 [46], [47]
LZU-190 400 1035 1.2 1.59 2.02 [48]
LZU-191 400 1305 2.3 1.13 2.38 [48]
LZU-192 400 706 1.3 0.45 2.10 [48]

Por-sp2c-COF 250 689 1.85 1.75 [49]

A2B2-Por-COF 400 785 2.0-2.3 [50]
CTF-Th 500 78 Mesoporous 2.48 [51]
CTF-Th-Ph 500 62 Mesoporous 2.42 [54]
asy-CTF 500 52 Mesoporous 2.30 [54]
COF-JLU22 510 945 2.36 1.03 2.08 [52]
OH-TFP-TTA 350-425 2122 1.3, 1.9 1.21 2.60 [53]
OH-TFP-TAPB 350-425 2051 1.6, 1.9 1.20 2.60 [53]
TTT-DTDA COF 450 1012 3.0-4.5 2.19 [56]
TTT-BTDA-COF 450 302 1.5-4.0 2.10 [56]
TpTt 200 277 1.3 2.74 [57]
Table 3. CO2 fixation reaction catalyzed by COFs.
Accepted Manuscript
COFs Conditions Substrates Yields Ref.
up to 95.8%
CTF-1 130 °C, 4 h [25]
at least 6 times
up to 99%
CTF-CSU19 TBAB, 25 °C, 48 h [58]
at least 5 times
up to 93.1%
CCTF-350 120 °C, 24 h [59]
at least 5 times
up to 99%
COF-IL 80 °C, 48 h [60]
at least 5 times
up to 98%
2,3-DhaTph TBAI, 110 °C, 12 h [62]
at least 5 times
up to 99%
COF-JLU7 TBAB, 40 °C, 48 h [63]
at least 5 times
OMe-OH-TPBP- up to 98%
TBAB, 40 °C , 24 h [64]
COF at least 5 times
other gases, such as methane, nitrogen or carbon

monoxide are seldom introduced to this system given to
2.3 Gas-storage properties of COFs in organic the challengeable nature of these reactions. Anyway, we
catalysis. are deeply convinced that the strategies used in CO2
fixation could provide us with new ideas to fix other
In this part, we use COFs to create an agreeable gases.
atmosphere for gas-based organic reactions, instead of Covalent triazine frameworks (CTFs), first reported by
utilizing the gas stored in COFs to catalyze the reaction. Thomas and co-workers, formed through the reversible
This means that the active sites are still acid, alkaline or iono-thermal trimerization of aromatic polynitriles. CTFs
metal units incorporated into COFs. The works reported hold great thermal and chemical stability owing to the
so far all encircled around the fixation of carbon high content of nitrogen atoms, which also provides
dioxide—from epoxides to cyclic carbonates. However, CTFs with alkalinity and the ability to coordinate with
15

metallic catalysts. Therefore, Thomas’s group CCTF-350 may displayed a lower surface area owing to
established two CTFs (CTF-1, CTF-P, Fig 5, Table 4) to its densely stacked 2D layer structure. In the following
work as efficient and effective base catalyst to help the year, Dong’s group and Wang’s group attached
conversion of CO2 with great activity (95.8 %) (Table imidazolium salts to the pore walls, instead of turning
3).[25] Through control experiments, the author found that them into linkers to build the COF (COF-IL, Fig 5, Table
amorphous CTFs (CTF-1-HAS, CTF-P-HSA) with 4). COF-IL possessed great catalytic activity in the
higher surface area and hierarchical porosity displayed conversion of CO2 (99 %).[60] In Dong’s work, the author
better catalytic activity than crystalline one. This result next attached COFs to thiol-based chitosan, a naturally
indicated that high surface area and hierarchical porosity occurring polymer, which then turned into a kind of
may take precedence over great crystallinity in this hybrid aerogel (COF-IL@chitosan). COF-IL@chitosan
reaction. Apart from that, it was reported that pKa has was robust and possessed high fabricability, this
nothing to do with the activity of amines in the promoted the author to fabricate a cuplike reactor. A
conversion of CO2, but stronger basicity did help CTFs scale-up reaction (up to 180 g) proceeded smoothly in
absorb more CO2 by fixing them as carbamates. Further this reactor and gained excellent yield (91%). Moreover,
studies are still needed, since the author cannot the hybrid aerogel could be reused by simply washing
discriminate the exact relevance among the basicity, and vacuum drying. Therefore, it is a successful example
Accepted Manuscript
crystallinity and activity of the CTFs, especially when of amplification in the reactions catalyzed by COFs.
none of these factors could be precluded. Similarly, Wang’s group also used similar COFs to turn
CTFs have the gift to stock CO2, since nitrogen atoms this reaction into an industrial scale. The reaction could
could function as CO2-philic sites as well as catalytic proceed without solvent and cocatalysts and achieve a
active sites. Yu and co-workers embraced carbazole unit turnover number of 495000. The different things are that
into CTFs (CTF-CSU1/19, Fig 5, Table 4) to they took the post-modification strategy to construct the
continuously increase the content of N atoms. [58] This COFs and further catalyzed the formation of amines with
approach helped the capture and conversion of CO2 under the conversion of CO2.[61]
atmospheric pressure and room temperature. An Both basic and acidic sites could promote the fixation
elaborated plausible mechanism was presented at the of CO2, former introduction all revolved around basic
same time (Scheme 20). Examples utilized imidazolium ones. Bhanage et al. reported 2,3-DhaTph as acidic ones
salts as supplementary tools to promote the to catalyze the fixation of CO2.[62] 2,3-DhaTph can also
cyclicaddition of CO2 via dipolequadruple interactions catalyze condensation reaction owing to its hydroxyl
were also explored in few works. Imidazolium salts draw groups. It is worth pointing that this reaction was carried
chemists’ attention owing to their abilities to work as out without solvent, but it needs phase transfer catalysts
green reaction solvents. Besides, they themselves are (TBAI, TBAB). Then, Liu’s group also reported two
classical homogeneous catalysts in the conversion of CO2. imine-linked COFs (COF-JLU6, COF-JLU7, Fig 5,
Therefore, the incorporation of imidazolium salt into Table 4) with high density of hydroxyl group to activate
COFs is a mutual enhancement for the fixation of CO2: epoxides through hydrogen-bond interaction. Triazine-
imidazolium salts help COFs do better in catalytic based cores were also introduced to strengthen the
activity and COFs help imidazolium salts enhance their storage ability for CO2, which further validates the value
reusability and recyclability. In 2018, Cao et al. found of triazine-based cores in this reaction.[63] A plausible
that CCTF-350 (CCTFs, Fig 5, Table 4) (synthesized mechanism of acid-catalyzed fixation of CO2 was
under relatively low temperature: 350 °C) had the highest proposed according to previous studies and experimental
density of active sites when compared with CTFs results (Scheme 20, b). Recently, Chen et al. also
synthsized in higher temperature, because higher established few hydroxyl-based COFs (OMe-OH-TPBP-
temperature will lead to decomposition of backbones.[59] COF, OH-TABP-COF, Fig 5, Table 4) and verified that
The density of active sites was a determined factor to hydroxyl groups were the active sites to catalyze the
overall catalytic efficiency, which made CCTF-350 the conversion of CO2.[64]
greatest catalyst among relating catalysts. Even though
Scheme 20. The CO2 fixation reaction in base (a)/acid (b) mechanism.
16

3. As supports of non-metal complexes

In this chapter, COFs mainly work as the supports of
various non-metal complexes, especially organocatalysts.
Studies in this area are still rare due to the dilemma in
COFs’ synthesis: the introduction of organocatalysts to
COFs by attaching them to organic precursors will
jeopardize or even sacrifice the stack model, crystallinity Scheme 21. Michael addition reactions catalyzed by [Pyr]x-
and then catalytic activity; besides, we cannot assure the H2P-COF (a) and [(S)-Py]x-H2P-COF (b).
ideal catalytic sites will be distributed uniformly by post-
modification method, this would also lead to
unsatisfactory catalytic activity. Hence, how to
effectively and efficiently integrate these non-metal
complexes as catalytic sites while maintaining the
Accepted Manuscript
stability and crystallinity of COFs is a critical problem.
3.1 “Post-modification” Strategy

The symmetric crystalline frameworks and asymmetric
chiral functional groups seem mutually exclusive to each Scheme 22. Asymmetry Michael addition reactions carried out
other. But if we guarantee the crystalline frameworks in continues flow condition.
first and then integrate organocatalysts into COFs with
efficient ways, this issue will be solved. In 2014, Jiang The defect in last work is clear: poor streoselectivity.
and co-workers first accomplished this task with click Therefore, Jiang’s group continued to explore and elevate
chemistry. [Pyr]x-H2P-COFs (Fig 6, Table 5) were the reaction in the following year. In this work, pure (S)-
synthesized and their catalytic activities were explored pyrrolidine units were anchored onto the channel walls
in asymmetry Michael addition reactions (Scheme 21, with the same method, which improved the
a).[26] In this work, ethynyl units were first incorporated enantioselectivity to great values (up to 92%) (Scheme
into building blocks with varying contents via pore 21, b).[65] COFs ([(S)-Py]x-H2P-COF, Fig 6, Table 5)
surface engineering as potential functional group. Then behaved the same as last one: highly dense catalytic sites
the fixation of pyrrolidine derivatives was done through led to the decrease in catalytic activity. It is worth to
the reaction between ethynyl units and azide compounds, mention that the reaction catalyzed by this COF
a classical reaction in click chemistry. The click proceeded under ambient and clean condition (neat
chemistry is agreeable for controllable introduction of water). More importantly, methoxy groups were
organocatalysts. It is understandable that both surface introduced as electron-donating groups to buffer the
area and pore sizes decreased as the pyrrolidine interlayer charge repulsion, this reinforced the interlayer
derivatives were increasingly anchored to 1D pore walls. interactions and greatly enhanced the crystallinity and
However, the steroselectivity of pyrrolidine derivatives stability of COFs: [(S)-Py]x-H2P-COFs remained intact
are largely dependent on their substitutions. Therefore, even when they were treated with aqueous HCl (12 M)
the simple pyrrolidine units in this case only showed and NaOH (14 M) for one week.
moderate steroselectivity (51 %) in this reaction. Attaching active sites to the structures of COFs is not
Although COFs in this work could not help to enhance the only way to functionalize COFs. Immobilizing
the steroselectivity, they did help shorten the reaction instead of fusing the catalytic sites is also a good choice,
time. We illustrated that high density of catalytic sites just like chemists immobilizing metals to COFs. In 2019,
enhance the overall catalytic activity in CO2 fixation in Yaghi’s group first developed an olefin-linked COFs
former part. However, this principle failed in this work (COF-701, Fig 6, Table 5), which was stable enough to
due to a steric congestion caused by highly dense serve as carrier of BF3, a strong Lewis
pyrrolidine units, which further hindered the mass acid.[66]Considering both Lewis acid and Lewis base
transport in the channels. Interestingly, a continues flow could promote the acceleration of Diels-Alder reaction,
reaction was carried out with a columnar setup in full the BF3-immobilized COF (BF3 ⊂COF-701) also showed
conversion and moderate streoselectivity (44 %) catalytic activity in DA reactions (Scheme 23).
(Scheme 22).
Scheme 23. Diels-Alder Reaction catalyzed by BF3 ⊂COF-701.

Accepted Manuscript
Fig 5. Structures of CTF-1/P, CTF-CSU1/19, CCTF, COF-JLU6/7, COF-IL, OMe-OH-TPBP-COF, OH-TPBP-COF.

Table 4. A summary of structure data of relating COFs mentioned in Gas-storage properties of COFs in organic catalysis.
TGA BET Surface Average Pore size Pore volume
COF Ref.
(oC) Area (m2g-1) (nm) (cm3g-1)
CTF-1 536 0.38 [25]
CTF-1-HSA 2087 1.30 [25]
CTF-P-HSA 200 1745 0.94 [25]
CTF-CSU1 400 685 1.0-1.3 0.36 [58]
CTF-CSU19 400 982 1.0-1.5 0.58 [58]
CCTF-350 [59]
CCTF-400 568 [59]
CCTF-500 1353 [59]
COF-IL 230 291 1.65-2.22 [60]
COF-
230 103.3 [60]
IL@chitosan
COF-JLU6 460 1450 3.1 0.96 [63]
Accepted Manuscript
COF-JLU7 407 1392 3.3 1.78 [63]
OMe-OH-TPBP-
433 501 1.4 [64]
COF
OH-TPBP-COF 346 200 1.6 [64]
introduces us the importance of choosing “platform

molecule”: well-chosen monomers enrich the
3.2 “Bottom-up” Strategy possibilities in the construction of CCOFs.
Actually, we have introduced this method in last chapter:

the direct incorporation of imidazolium ionic salts to
serve as linkers or attached them to linkers (pore walls)
to catalyze the fixation of CO2, both methods performed
“bottom-up” strategy. The different thing is that we are
going to center on the building of chiral organocatalysts
in this section. In the transition-metal-based asymmetric
organic reaction, chemists always use ligands with giant
steric hindrance to assist the formation of chiral centers
effectively. However, such bulky spatial hindrance will Scheme 24. Asymmetric aldol reaction catalyzed by LZU-76
deteriorate the highly-ordered structures and crystallinity (a) and asymmetric amination of β-ketoesters catalyzed by
of COFs to a large extent. Therefore, the careful chosen TAH-CCOFs (b).
of functional organic precursors will be a fundamental
but vital issue in bottom-up” strategy.
Wang and co-workers first constructed two COFs
(LZU-72, LZU-76, Fig 6, Table 5) with L-proline in
direct synthetical way to catalyze the asymmetric Aldol
reaction with great yields (up to 84 %) and
streoselectivity (Scheme 24, a).[67] Another crucial point
lies with the rigid framework of COFs: only robust Scheme 25. The multi-connectivity and functionality of
scaffold could resist the potential damage brought by new DBCBI.
attachments. In this work, Wang demonstrated us two
indispensable factors that need us to consider in this
straightforward strategy: the judicious design of chiral How to strike the balance between asymmetric
precursors and rigid frameworks. In 2019, another group organocatalysts and symmetric crystallinity? It is still a
developed a general method to construct a series of chiral knotty problem even though we are aware of what giant
COFs (MH-CCOFn, TAH-COFn, SAH-CCOF1-Boc, G- organocatalysts will bring. Therefore, sometimes the
CCOF1, Fig 6, Table 5) in the same platform through a seemingly tedious method may become the most efficient
strategy called “divergent synthesis”.[68] In this strategy, way for us to deal with it, especially when we do not have
pre-chiral monomers DBCBI (Scheme 25) could be systematic guidance.
installed with various chiral organocatalysts and
connectors in different ways to fit in each framework.
With these CCOFs in hands, the author further screened
them in asymmetric amination of β-ketoesters (Scheme
24, b) and harvested excellent yields (up to 96 %) and
enantioselectivity (99 %) (Scheme 24). This work

3.3 As supports of linear polymers.
Scheme 26. α-Aminooxylation of aldehydes (a) and aldol

reactions (b) catalyzed by CCOFs.
Cui’s group adopted a multivariate strategy to Scheme 28. CO2 fixation reaction (a) and asymmetric aldol
establish a series of chiral COFs (DMTA-TPBn, DMTA- reaction (b) catalyzed by PPS⊂COF-TpBpy-Cu and CP@COF.
TPBn', DMTA-TPB1/n, DMTA-TPB1/n', Fig 6, Table 5)
to catalyze asymmetric α-aminooxylation of aldehydes,
Accepted Manuscript
aldol reactions and Diels-Alder reactions with good If we imagine those active sites as paintings
yields (up to 95 %) and enantioselectivities (95 %) decorated on the walls, then linear polymers are more like
(Scheme 26, a, b).[42] This work enables us to learn deeper many strands of coloured LED bulbs hanging in the room.
between properties and structures of COFs: the For the purpose of establishing multifunctional catalysts
introduction of organocatalysts, especially with bulky with cooperative active sites, Cui and co-workers
groups, will lead to the decrease of π-π interactions of threaded polymerized phosphonium salt into COFs
interlayer and then the chemical stability and crystallinity. (PPS⊂COF-TpBpy-Cu, scheme 29) and integrated
This could be neutralized by tailoring the density of bipyridine as the coordination sites of Cu2+ to catalyze the
organocatalysts. For instance, CCOFs with three CO2 fixation reaction (Scheme 28, a).[70] The movability
components (DMTA-TPB11-x/2x) showed better of linear polymers endows themselves with similar
chemical stability than CCOF with two components properties as their homogeneous counterparts, but also
(DMTA-TPB2); apart from that, unprotected brings them problems like potential leaching. Fortunately,
organocatalysts will interact with the groups with lone leaching experiments indicated that no clear leaching
electrons in the 2D layers, such as methoxy and imine phenomenon was observed according to static solid-state
31
groups. The strong supramolecular interaction between P NMR spectroscopy and ICP-OES results. This result
them would imperil the interlayered interactions and then further proved the stabilizing ability made COFs become
made the CCOFs lose their crystallinities and catalytic favorable supports. Except that, the flexibility of PPS was
activities. Besides, CCOFs in this work demonstrated validated to be conducive for the overall catalytic activity,
close or even better catalytic activities than their which enabled the COF to have a high value of TON
homogeneous and heterogeneous counterparts. Another (over 20000). A Lewis acid-catalyzed CO2 conversion
example in this straightforward method was still mechanism was also proposed (Scheme 30).
exploited by Cui and co-workers, derivatives of DHIP Another work was also established by Cui and co-
and imidazolidine moieties were incorporated into COFs workers, chiral polymers were introduced to COFs
(TPB2-COF, Tfp2-COF, Fig 6, Table 5) to catalyze (CP@COF) as active sites to catalyze asymmetric aldol
asymmetric Steglich rearrangement and asymmetric reaction with excellent yields (up to 98 %) and
Michael addiction reactions in good yields (up to 95 %) stereoselectivity (99 %) (Scheme 28, b).[71] Interestingly,
and stereoselectivity (86 %) (Scheme 27, a, b).[69] MOF (CP@MOF) was also utilized as support of the
Anyway, we can find that examples in this area are still same chiral polymers in this work, and CP@COF showed
so rare that it is hard to meet the requirement for further superior catalytic performance and enantioselectivity
establishment of comprehensive catalytic system, let than CP@MOF. The author attributed this phenomenon
alone applications in industrial scale. to the synergistic effects of hydrophobic blocks in COF’s
channels: an oil-water interface was formed in
hydrophobic 1D channel, which increased the
concentration of reactants around active sites and then
accelerated the overall process. Besides, cage-like pores
in MOFs are distinguished from road-like channels in
COFs, the latter share more commons with homogeneous
catalysis.
Scheme 27. Asymmetric Steglich rearrangement (a) and

Asymmetric Michael addiction reactions (b) catalyzed by
TPB2-COF and Tfp2-COF.
20

Accepted Manuscript
Scheme 29. (a) The concept of heterogeneous concerted catalysis between active sites on the porous materials and highly flexible
linear polymers and schematic of PPS⊂COF-TpBpy-Cu synthesis (b) and structures of COF-TpBpy and PPS⊂COF-
TpBpy-Cu (c). Reproduced with permission. Copyright 2016, American Chemical Society.
racemic 1-phenylethanol reaction catalyzed by lipase@COF-

OMe. Reproduced with permission. Copyright 2018, American
Chemical Society.
If it remains tough to create stable man-made analogue

of enzymes, then maybe the easiest way is to protect them
with various materials. The poor stability and
recyclability of enzymes are always the holdbacks for
further utilization. COFs are exactly great tools to deal
with this problem. Ma and co-workers first immobilized
lipases into diverse COFs to catalyze the kinetic
resolution of racemic 1-phenylethanol reactions (Scheme
31).[28] Compared to other materials like mesoporous
silica and MOFs, COFs demonstrated higher lipase PS
Scheme 30. The potential mechanism of CO2 fixation reaction uptake capacities owing to their highly-ordered
catalyzed by Lewis acid. constructs with uniformly open pores. Besides, the author
also found that COFs with different adjunct groups
presented distinct abilities in enzyme up-take owing to
3.4 As supports of enzymes the host-guest interactions: the hydrophobic environment
in COFs is conducive for the infiltration of lipase PS.
This means that the adsorption of lipases on hydrophobic
support was a simulation of interfacial activation, a
ubiquitous phenomenon in lipases to turn them into open
state. However, high hydrophilicity of COFs would
compromise the activities of enzymes, but they are still
more active than free enzymes in harsh condtions. Most
importantly, the shield effect provided by COFs enabled
enzymes to maintain the majority of activities when they
were treated with polar solvents, relatively high
temperature or other rigorous conditions. Anyway, the
utilization of COFs in enzyme catalysis makes a
difference, enabling enzymes reaching their potential in
practical application.
Scheme 31. (a) Schematic illustration of the translocation of

enzyme into the pore channels. (b) Kinetic resolution of

Table 5. A summary of structure data of relating COFs as supports of non-metal complexes
BET Surface Area Average Pore size Pore volume

COF TGA ( °C) Ref.
(m2g-1) (nm) (cm3g-1)
[Pyr]0-H2P-COF 1126 2.2 [26]
[Pyr]25-H2P-COF 1092 2.0 [26]
[Pyr]50-H2P-COF 859 1.9 [26]
[Pyr]75-H2P-COF 324 1.5 [26]
[Pyr]100-H2P-COF 206 1.5 [26]
[(S)-Py]0.17-TPB-DMTP-COF 400 1970 3.07 1.13 [65]
[(S)-Py]0.34-TPB-DMTP-COF 400 1802 2.95 1.04 [65]
[(S)-Py]0.50-TPB-DMTP-COF 400 1612 2.86 0.83 [65]
COF-701 400 1366 1.14 [66]
LZU-72 185 1114 1.2-2.2 0.98 [67]
Accepted Manuscript
LZU-76 186 758 1.2-2.2 0.66 [67]
MH-CCOF1 200 680 2.9 0.65 [68]
MH-CCOF2 280 507 2.7 0.50 [68]
MH-CCOF3 280 316 2.9 0.35 [68]
MH-CCOF4 200 215 2.7 0.18 [68]
TAH-CCOF1 240 406 2.7 0.65 [68]
TAH-CCOF2 205 534 2.7 0.87 [68]
SAH-CCOF1-Boc 190 407 2.7 0.35 [68]
G-CCOF1 350 809 2.9 0.66 [68]
DMTA-TPB1/2' 300 1947 2.7 [42]
DMTA-TPB1/3' 300 1689 2.7 [42]
DMTA-TPB1/4' 300 1772 2.7 [42]
DMTA-TPB1/5' 400 1903 2.7 [42]
TPB2-COF 370 418 1.63 0.63 [69]
Tfp2-COF 370 362 1.67 0.49 [69]
COF-TpBpy 1497 [70]
PPS⊂COF-TpBpy 360 789 [70]
PPS⊂COF-TpBpy-Cu 496 [70]
CP@COF 300 128 0.6-1.2 0.36 [71]
COF-OMe 1740 3.3 1.62 [28]
lipase@ COF-OMe 784 3.3 0.59 [28]
4 As Supports of Metal Complexes immobilizing metal complexes to various materials like

zeolites, metal-organic frameworks (MOFs) and porous
Transition metals are also important in organic catalysis, organic polymers (POPs) and thereby turning them into
many of them are systematically and comprehensively heterogeneous catalysis. Zeolites are the cores of
studied for decades. Hence, the incorporation of metals industrial catalysis. COFs are also called “organic
into COFs to catalyze organic reactions was naturally zeolites” due to the similarities to zeolites. In this chapter,
studied and widely developed. The homogeneous nature literatures are categorized according to the organic
of these metal complexes always leads to problems like reactions catalyzed by COFs.
heavy metal pollution and low economic benefits.
Methods for solving these problems attract the attention
from many chemists. The most direct way is

Accepted Manuscript

Accepted Manuscript
Fig 6. Structures of [Pyr]x-H2P-COF, [(S)-Py]x-H2P-COF, COF-701, LZU72/76, CCOFs, DMAT-TPB1/n', TPB2-COF, Tfp2-
COF, COF-TpBpy and COF-Me
24

Ru/CTFs (Fig 7, Table 6) were utilized by Palkovits and

co-workers to catalyze selective aerobic oxidation of
4.1 Oxidation reaction HMF to DMF and exhibited better activity and
recyclability than its counterparts, such as Ru/C and
Ru/γ-Al2O3 (Scheme 32, d). However, the author found
that both substrates and products could be adsorbed and
were inclined to polymerize, which further decreased the
overall yields. The recycling tests suggested that
Ru/CTFs gradually lost their catalytic activities due to
polymeric surface and partial oxidation of NPs.
Accepted Manuscript
Scheme 32. Selective oxidation of methane, glycerol, benzyl
alcohol and HMF catalyzed by Pt-CTF (a), Pd/CTF (b) and
Ru/CTF-a (c), respectively.
The first example of organic reaction catalyzed by

COFs is an oxidation reaction (Scheme 32, a). In 2009, Scheme 33. Intramolecular oxidation of biaryl and selective
Ferdi and co-workers immobilized Pt2+ into CTFs (Pt- oxidation of olefins catalyzed by Pd(II)TpPa-1 (a), Cu-TAPT-
CTF, Fig 7, Table 6) using the coordination ability of DHTA-COF (b) and [Mn(bpy)2]-Dha Tab COF (c).
abundant N atoms in CTFs.[24] Given the strong bonds in
methane, further conversions are often confronted with
problems like harsh conditions, poor selectivity and low In 2014, Banerjee et al. reported a COF (TpPa-1, Fig
efficiency. In this case, the conversion from methane to 7, Table 6) as the support of Pd0 and Pd2+ to catalyze an
methanol proceeded in relatively low temperature with intramolecular oxidation of biaryl (Scheme 33, a), Heck
the help of Pt-CTF and H2SO4 and achieved great TON reaction and Sonogashira reaction, which we will
(300). Interestingly, compared to prepared Pt-CTF, the illustrate in the “C-C coupling reaction” part.[74]
direct addition of K2[PtCl4] and CTF to the reaction The combination of metal complexes and versatile
mixture needed several recycles to reach the same building blocks of COFs creates more possibilities. The
catalytic activity as prepared one. The author assumed same substrate could be converted into different products
that platinum species needed to rearrange uniformly after when various metal complexes are introduced into COFs.
first coordinating. In 2017, Chen’s group coordinated Cu2+ into an imine-
There are various sensitive functional groups in linked COF (TAPT-DHTA-COF, Fig 7, Table 6) to
organic compounds, therefore, chemoselectivity is catalyze the selective oxidation of olefins (Scheme 33,
always a prior problem that needs solve. In the following b).[75] Interestingly, COFs synthesized in different
year, Thomas et al. incorporated Pd2+ into CTFs to solvents exhibited distinct stabilities and catalytic
catalyze the selective liquid phase oxidation of glycerol activities. Cu-COFHX (synthesized in dichlorobenzene
(Scheme 32, b).[72] When compared to activated carbon and n-butanol) showed higher crystallinity, stability,
(Pd/AC), Pd/CTF (Fig 7, Table 6) showed slightly better surface area and even better selectivity in oxidation
selectivity and catalytic activity, but the recyclability was reaction, when compared with Cu-COFDMF (synthesized
hugely improved. Then, Thomas’s group continued to in DMF). In the following year, Gao and co-workers
explore in this field. With the same CTF (Pd/CTF) in established an ionic sulfoacid-based COF ([SO3H]-
hands, the author further utilized them to catalyze the DhaTab, Fig 7, Table 6) and decorated it with
selective oxidation of benzyl alcohol with O2 as oxidant [Mn(bpy)2]2+ via “post-modification strategy” to catalyze
(Scheme 32, c).[73] It was found that metal immobilization the epoxidation of olefins (Scheme 33, c).[76] It is obvious
process could be enhanced by introducing nitrogen atoms that the “post-modification” strategy and “bottom up”
into the frameworks, which limited the size of strategy are fundamental methods to construct any
nanoparticles (NPs) and thereby improving the catalytic functional COFs, they were used not only in the
activity. We have introduced a reaction that converted development of organocatalysts-based COFs, but also in
fructose to HMF or DMF in the second chapter.[34] metal-docked COFs et al.
Similarly, through immobilizing Ru NPs into CTFs,

Accepted Manuscript
Fig 7. Structures of Pt-CTF, (Pd)-CTF, Ru/CTF-a, Pt@COF, TpPa-1, TAPB-DHTA-COF, [SO3Mn]-DhaTab, and VO-TAPT-
2,3-DHTA COF.

Table 6. A summary of structure data of relating COFs in oxidation reaction.

COF TGA (oC) Ref.
(m2g-1) (nm) (cm3g-1)
CTF 400 1061 1.4 0.934 [24]
Pt-CTF [24]
CTF 2814 1.79 [72]
Pd-CTF 2490 1.56 [72]
Ru/CTF-a 2439 1.96 [73]
TpPa-1 484 1.78 0.546 [74]
Pd(0)@ TpPa-1 226 1.60 0.269 [74]
Pd(II)@ TpPa-1 195 1.25 0.214 [74]
TAPT-DHTA-COFHX 450 2238 1.29 [75]
TAPT-DHTA-COFDMF 300 660 0.56 [75]
Cu-COFHX 1886 1.11 [75]
Accepted Manuscript
Cu-COFDMF 366 0.41 [75]
DhaTab 300 1312 3.4 [76]
[SO3Mn]-DhaTab 300 477 1.6 [76]
TAPA-2,3-DHTA COF 1151 3.0 [77]
VO-TAPA-2,3-DHTA
400 562 2.5 [77]
COF
Pt@COF-Annealed 350 [78]
Different metal-based COFs could also catalyze the

same reaction. Recently, both Ma’s group and Alemán’s
group reported a COF-catalyzed sulfide oxidation
reaction with different strategies (Scheme 34, a, b).[77-78]
In Ma’s report, two ortho-hydroxyl groups were
introduced into COFs (VO-TAPT-2,3-DHTA COF, Fig
7, Table 6) to coordinate with VO2+ in traditional way,
which then catalyzed the sulfide oxidation with t-
BuOOH as oxidant. Plausible mechanism was also
studied (Scheme 35). In Jose’s work, Pt2+ was
incorporated into COFs (Pt@COF, Fig 7, Table 6) as
photosensitizer through monomer truncation strategy to
catalyze visible-light-induced sulfide oxidation reactions
and hydrodebromination reactions. Instead of
coordinating to entire whole COFs, Pd2+ complexes were Scheme 34. The oxidation of sulfide and hydrodebromination
used to block one of the linking points of monomers, reaction catalyzde by VO-TAPT-2,3-DHTA COF (a) and
which were used in following constructions of COFs. Pt@COF (b).
Such method gave rise to randomly distributed structural
defects and low incorporation of Pd2+ complexes (due to
the self-healing nature of reversible bonds) in the
frameworks, but also made it much easier to immobilize
metal complexes into COFs. Besides, it was found that
conjugation of frameworks and the particle size of
materials were crucial in this system through the
comparison between Pt@COF and Pt@COF-Annealed.
Scheme 35. Proposed mechanism of oxidation of sulfide.

Catalyst Condition Reductant Yield/ Recyclability Ref.

Au(0)@TpPa-1 99%, At least 6 times [79]
Au(0)@TAPB-DMTP-COF 99%, At least 6 times [80]
Fe3O4@COF-Au r.t., H2O NaBH4 99%, At least 6 times [81]
CuFe2O4/Ag@COF 99%, At least 6 times [82]
PtNPs@COF 99%, At least 6 times [83]
Scheme 36. The reduction of 4-nitrophenol catalyzed by various metal-based COFs.
Accepted Manuscript
(15 nm) in COFs (0.10 and 0.20 wt%) exhibited better
catalytic activities than Au NPs (50 nm) in COFs (0.38
4.2 Reduction reaction wt%). Another work also took this encapsulation
strategy to design a core-shell structure, which has
We have introduced some reduction reactions in been introduced one in the second part.[41] Recently,
previous sections, such as the fixation of CO2 reactions Lu et al. encapsulated magnetic Fe3O4 NPs as cores of
and hydrodebromination reactions catalyzed COFs. In COF (TAPB-DMTP-COF, Fig 8, Table 7), and then
this section, we are going to discuss some reduction immobilized Au NPs into the shell layers of COF to
reaction catalyzed by metal complexes in COFs. catalyze this reduction reaction with NaBH4 as
Metals like Pd and Pt are widely used in the industrial reductant and reaped great yields (up to 99 %)
reduction reactions. Therefore, it is nature for us to (Scheme 36). [81] Although Fe3O4 NPs demonstrated no
incorporate them into COFs for enhanced recyclability enhancement to the catalytic activity of Au NPs, they
and economic benefits. The majority of works in this did help to recycle the catalysts much easier via their
section are related to the reduction of 4-nitrophenol to magnetic property. Similarly, Liang’s group also
4-aminopheol with H source like NaBH4 and N2H4. 4- reported a work that took the core-shell strategy and
Nitrophenol is a toxic environmental pollutant; on the introduced (TAPB-DMTP-COF) as the shell,
contrast, 4-aminopheol is a crucial industrial raw magnetic PVP-modified CuFe2O4/Ag NPs as the core
material. In 2014, Banerjee first reported an Au-loaded to catalyze the reduction reaction (Scheme 36).[82] In
COF (Au(0)@TpPa-1, Fig 8, Table 7) with enhanced this work, both CuFe2O4 NPs and Ag NPs helped to
stability and reusability of Au NPs and activity for transfer the electrons and the CuFe2O4 NPs prevented
nitrophenol reduction (Scheme 36).[79] Metal Ag NPs from aggregation. COFs also functioned as the
nanoparticles in COFs generally form through the platform to stabilize metal NPs and supplied additional
reduction from metal ions with strong reductants like channels to transfer substrates. The overall combined
NaBH4, which may cause harm to the crystallinity and merits enhanced the catalytic activities of such core-
integrity of COFs. Therefore, concerns about leaching, shell frameworks.
sintering, aggregating, and recyclability of NPs and the The strategy to encapsulate large size metal NPs
chemical stability of COFs are the priorities for into COFs has been introduced, next we are going to
chemists to handle. In this case, Au NPs in size of 5±3 present the method of immobilizing small size NPs
nm were uniformly distributed into a stable COF into COFs. The majority of NPs that were introduced
without obvious leaching and aggregating into COFs generally possess large size with broad size
phenomenon. It is worth pointing that a relatively low- distribution(Au NPs: 5±3 nm, Pd NPs: 7±3 nm). As
loaded (1.20 wt%) Au(0)@TpPa-1 exhibited higher compared to the pore size of COFs (0.5-4 nm), those
catalytic activity than high-loaded (2.20 wt%) one. NPs were mainly fixed between two layers rather than
This result was attributed to the fine distribution of Au in pores walls, which is unfavourable for catalytic
NPs in the low-loaded one. In 2017 Lu’s group also activities and chemical stabilities of COFs due to the
reported an Au-loaded COF (TAPB-DMTP-COF, Fig weak interactions between metal NPs and frameworks
8, Table 7) to catalyze this reaction with nearly of COFs. Zhang and co-workers established an COF
quantitative yield (up to 99 %) (Scheme 36).[80] On the (Thio-COF, Fig 8, Table 7) with thioether group to
contrast, Au NPs were synthesized first and modified serve as template to help noble-metal NPs grow
by polyvinylpyrrolidone (PVP), an amphiphilic uniformly in narrow size distribution (1.7±0.2 nm).[83]
surfactant used to help NPs disperse well in polar Not surprisingly, Pt NPs in Thio-COF finished the
solvents. Then, the nucleus of COFs were grown on reduction reaction with lower loading and shorter time
the top of the surface of the PVP-modified NPs. This to when compared to previous reports. Therefore, this
encapsulation strategy enables COFs to remain stable work tells us that introducing and tuning the functional
and crystalline and supplies a new way to immobilize groups is an effective way to tailor the properties of
large-size NPs into COFs. Interestingly, the catalytic NPs, and thereby the following catalytic activities.
control experiments matched former results: Au NPs
28

Besides Au and Pt, Pd is also a classic catalyst in

reduction reaction. In 2016, Vasile constructed an
adamantane-based 3D COF (Pd/COF, Au/COF, Fig 8,
Table 7) to sever as the support of Pd and Au to
catalyze selective reduction of nitrostyrene with H2.[84]
Compared to Au NPs, Pd NPs showed better
chemoselectivity and catalytic activity (Scheme 37, a).
Interestingly, the alteration of solvents could also Scheme 38. The reduction of N-methylpyrrole (a) and 1,10-
change the chemoselectivity. The author also used phenanthroline (b) catalyzed by Pd/CTF-1.
Pd/COF to catalyze the hydrogenation of various nitro
compounds, but all of them showed poor conversions.
Similarly, Wang et al. reported a Pd NPs loaded CTF In 2018, Vaidhyanathan et al. reported a
to catalyze the hydrogenation of various nitro Co/Co(OH)2 NPs-loaded COF(IISERP-COF5, see
compounds (Scheme 37, b) with formic acid as the COF-JLU5, Fig 4, Table 2) for the reduction of nitrile
source of H and reaped excellent conversions (99 %) compounds under mild condition (Scheme 39, a).[87]
Accepted Manuscript
and selectivity in 2018.[85] As we have mentioned The triazine-based core was also incorporated to help
previously, the high contents of nitrogen atoms in Co/Co(OH)2 NPs distribute evenly and robustly into
CTFs not only stabilize the frameworks but also serve COFs. The cyclic voltammogram suggested that the
as great platform to coordinate with metal ions, which reaction proceeded through a redox mechanism with
is agreeable for further reduction to metal NPs. the Co2+/ Co3+ couple, which was similar to the
Therefore, Pd NPs also possessed a narrow size reaction catalyzed by unsupported cobalt salts but with
distribution (4.25±0.43 nm) in this work, which laid a enhanced catalytic activities. Recently, Gao’s group
solid foundation to its high catalytic activity. Not also incorporated Co2+ into COFs (TFPPy-PyTTA
surprisingly, the majority of the substrates could be COF, Fig 8, Table 7) via a post modification method
reduced with almost full conversion and excellent that we have introduced previously: sulfonic acid
selectivity in less than one hour with turnover number groups were anchored to the linkers after the reduction
up to 495 per hour. of imine bonds, and then Co2+ were immobilized
through the metathetical reaction with sulfonic acid
groups.[88] The catalytic performance of such
combination was evaluated through catalyzing the
fixation of CO2 with excellent yields (up to 97 %) and
recyclability (Scheme 39, b).
Scheme 37. The reduction of nitrostyrene and nitro

compounds catalyzed by Pd/Au/COF (a) and Pd@CTF (b).
After the introduction of the hydrogenation of nitro

compounds, we next move to other unsaturated Scheme 39. The reduction of nitrile compounds (a) and CO2
organic compounds. Both CTF-1 and Pd NPs were (b) catalyzed by Co@COF and Co2+@ TFPPy-PyTTA-COF.
introduced in former chapter,[25] in 2015 Chen and co-
workers reported the Pd/CTF-1 catalyzed
hydrogenation of N-methylpyrrole and 1,10- Aforementioned conversions of CO2 always involve
phenanthroline with H2 (Scheme 38).[86] This work with the process from epoxides to cyclic carbonates.
further validated the high nitrogen contents in CTFs Recently, Manirul’s group accomplished the N-
did enhance the catalytic activity: not only through Methylation of amines and the preparation of
providing anchoring sites for metal NPs (which carbamates through the fixation of CO2 (Scheme 40)
enabled NPs to distribute uniformly into COFs) , but catalyzed by a Zn2+ loaded COF (TFP-DAQ COF, Fig
also via working as electron donors to increase the 8, Table 7),[89] respectively. Polymethylhydrosiloxane
electron density of metal NPs (which facilitates the (PMHS) was used as the reductant to finish the
transmission of substrates and products). Moreover, in selective reduction reactions under mild conditions.
the hydrogenation of 1,10-phenanthroline, a selective
hydrogenation could be achieved by altering the
pressure of H2. However, the catalytic activity dropped
quickly after three recycles, which was blamed for the
poisoning effect caused by N-contained substrates.
29

Scheme 42. Reductive cleavage of C-S bonds catalyzed by

Ni-DBA-2D-COF.
Scheme 40. The N-methylation of amines catalyzed by
Zn(II) TFP-DAQ COF. 4.3 Coupling reaction
Cross-coupling reactions catalyzed by transition-
The removal of heteroatoms, like halogen and sulfur, metals are the cornerstones of modern synthetic
from toxic compounds is a productive way to convert chemistry. The synthesis of complex nature products
organic pollutants into useful molecules. In 2018, and medicine molecules are heavily relying on them
Accepted Manuscript
Dong and co-workers reported an interesting work: Pd owing to their powerful abilities to construct C-C
NPs were encapsulated into COF (COF-AO, Fig 8, bonds, C-N bonds et al. with high chemoselectivity
Table 7) to catalyze the dehalogenation of p- and steroselectivity. However, the high cost of the
chlorophenol in water with HCO2NH4 as the reductant transition-metals and the ligands, as well as the heavy
(Scheme 41).[90] The interesting part is that the author metal residue limit the utility of transition-metal-
fabricated an covalent cross-linked COF membrane catalyzed cross-coupling in industry. This problem
via postsynthetic covalent copolymerization strategy: could be solved perfectly through incorporating
alkenes groups were firstly installed as pre-functional transition-metals into COFs.
groups into building blocks. After that, Pd NPs-loaded
COF was attached to thiol-decorated polysiloxane
through a photo-induced thiol-ene click reaction. Such 4.3.1 Suzuki-Miyaura reaction, Heck reaction
membrane was utilized to establish a continuous-flow and Sonogashira reaction.
setup with a pump and simulate an industrial water-
treatment equipment. More amazingly, although such The Suzuki reactions generally involve a classical Pd0/
membrane-based microreactor finished the reaction Pd2+ catalytic circles, which has become a universal
with prolonged time, the product was obtained in great mechanism in many coupling reactions. Wang and co-
yield (94%) was obtained, which displayed its workers first immobilized Pd into COF (COF-LZU1,
potential practicality. Fig 9, Table 7) to catalyze the Suzuki-Miyaura
reaction with excellent yields (up to 98 %) (Scheme 43,
a).[15] Actually, imine-type ligands themselves are
simple but versatile ligands in coordination chemistry,
which had been widely used in homogenous catalysis.
Therefore, the imine-linked COFs are also simple
examples of designing ligands into COFs. The
Scheme 41. Dehalogenation of p-chlorophenol catalyzed by
layered-sheet structures of the frameworks possess
Pd@COF-AO.
two N atoms with an optimal distance (~3.7 Å) to form
a robust coordination bond with Pd2+, thus enhancing
its chemical stability and catalytic ability (Scheme 44).
The last reaction we are going to introduced in this
Besides, further leaching experiments also validated
part is the reductive cleavage of C-S bonds (Scheme
the strong interactions between COF and Pd2+.
42) catalyzed by a Ni NPs-loaded COF (DBA-COF 5,
Similarly, Jiang et al. also took imine bonds as linkers,
Fig 8, Table 7). Mc Grier et al. designed
and incorporated porphyrins as knots to construct a
dehydrobenzoannulene (DBA) monomers into COFs
COF (H2P-Bph-COF, Fig 9, Table 8) in 2015. [92]
as the coordinate sites of Ni NPs. As a result, both Ni-
Porphyrins have been introduced early in the
DBA[12] (monomer) and Ni-DBA-2D-COF
condensation reactions based on their alkalinity, but
manifested catalytic activity in the reduction reaction,
they themselves are nature ligands which we cannot
among which the monomer performed better in the
live without—the heme in our body from the
majority of situations.[91] And of course, COFs’
chlorophyll in plants. Therefore, porphyrins are great
superiority lies with their recyclability. Besides, it is
scaffolds for versatile metal-based COFs’ catalysis.
worth mentioning that DBAs could also coordinate
And of course, this nitrogen-rich porphyrin-based
with other earth-abundant metals like Co and Fe, both
COF exhibited excellent catalytic activity (98.5%),
of which are powerful metals in organic synthesis. It is
especially when compared with Pd/C, Pd-MOF,
a classic strategy that incorporating metals into COFs
Pd@SiO2 and other heterogeneous catalysts (Scheme
through designing various organic ligands into COFs,
43, b).
thus endowing COFs with corresponding catalytic
abilities of metals.
30

We have introduced the PtNPs@Thio-COF in the

reduction reaction, in the same work, Zhang et al. also
immobilized Pd NPs into Thio-COF to catalyze
Suzuki-Miyaura reaction (Scheme 46, a).[83] Given the
ultrafine Pd NPs with narrow size distribution,
PdNPs@Thio-COF presented high catalytic activity:
the coupling reactions were finished with extremely
low contents of Pd (0.1 mol% Pd Cat.) in a short time,
and achieved high yields (up to 99 %) at the same time.
Scheme 43. Suzuki-Miyaura reaction catalyzed by Pd/COF- This result was even better than classic Pd catalysts
LZU1 (a) and Pd/H2P-BpH-COF (b). like Pd(PPh3)4 and Pd(PPh3)2Cl2. In the same year,
Ramaswamy and co-workers also developed two
COFs (TAT-DHBD, see COF-JLU6, Fig 5, Table 4,
TAT-TFP, Fig 9, Table 8) to immobilize Pd/Pd2+ and
catalyzed the Suzuki reaction (Scheme 46, b).[94]
Accepted Manuscript
Interestingly, Pd in these COF exhibited better
selectivity and catalytic activities in substrates with
electro-withdrawing groups. As for electro-donating
groups, only medium conversions and selectivity were
obtained, which was different from works introduced
Scheme 44. The coordination of Pd (II). before. Unfortunately, the activity decreased about 20
percent after five recycles.
In the following year, Pierre’s group established a

Pd2+-based 3D COF (COF-300, Fig 9, Table 8) to
catalyze Suzuki-Miyaura reaction under mild
condition and achieved excellent yields (up to 95%),
with TOF up to 3000 per hour.[93] In Wang’s work in
2011,[15] harsh conditions like high temperature (p-
xylene at 150 °C) were needed, which led to partial
damage to the crystallinity and integrity of the
framework. Therefore, mild conditions are desired for Scheme 46. Suzuki-Miyaura reaction catalyzed by Pd
maintaining the structural regularity and recyclability. NPs/Thio-COF (a) and Pd(II)/Pd(0)TAT-DHBD/TAT-TFP
In this work, the reaction could proceed under low (b).
temperature with short reaction time. High yields of
product were obtained at the same time (Scheme 45,
a). Besides, more than 40 substrates were tested to
verify the broad substrate scope. Through tailoring the
reaction conditions, Pd(OAc)2@COF-300 could also
catalyze Heck reaction and Sonogashira reaction with
great yields (up to 90 %) (Scheme 44, b, c).
Scheme 47. Suzuki-Miyaura reaction catalyzed by Pd

NPs/Phos-COF-1 (a) and cascade reaction catalyzed by
PdAu NPs@Phos-COF-1 (b).
Many ligands were introduced to COFs, both simple

and complex one. Recently, Zhang et al. constructed
COF (Phos-COF-1, Fig 9, Table 8) based on PPh3, a
classical ligand of Pd. Such building block could
function as the thioether group, which was reported by
author to control the growth of metal NPs in narrow
size distribution in 2017. Metal NPs in this work also
Scheme 45. Suzuki-Miyaura reaction (a), Heck reaction (b) achieved similar narrow size distribution,
and Sonogashira reaction (c) catalyzed by PdNPs@Phos-COF possessed great catalytic ability in
Pd(OAc)2@COF-300. Suzuki reaction and Au/PtNPs@Phos-COF worked
the same in the reduction of 4-nitrophenol (Scheme 47,
a, b).[95] Given this situation, bimetallic NPs loaded
31

COF (PdAuNPs@Phos-COF-1) was synthesized to chemical composition analyses, Pd@COF (TAPB-

catalyze a tandem cross-coupling and hydride BTCA, Fig 9, Table 8) synthesized in In-situ method
reduction with a total yield of 60%. Oddly, the possessed higher loadings of Pd, indicating a better
oxidation state ration of P atoms decreased with the metalation efficiency. Although both them exhibited
increase oxidation state ration of Au, which indicated similar catalytic activities in Suzuki reaction, it was
a corresponding redox reaction between P and Au with found that palladium favored the amine-defects caused
Pd as the catalyst. The exact reason for this by the structural rearrangements. This referred to the
phenomenon is still unknown, therefore, further crystallizing and tautomeric forming process, which
investigations are still needed. enhanced the stability of Pd2+ active sites in COFs.
Another work developed a new method to construct This assumption was also verified by further DFT
a series of hierarchically porous COFs (HP-COFs).[96] calculations: defective structures were much stable
In this report, Wang’s group synthesized COF in ionic and energetically favourable for metalation process
liquids (ILs). Ionic liquids could be adjusted by compared to defect-free system. The author also
changing the alkyl chain length and thereby tuning the investigated other phenomenon, such as how
pore size of COFs. Ionic liquids worked as template palladium (II) bromide species formed in the reaction.
Accepted Manuscript
for COFs to grow on and would be removed after For more details, please see the original paper.
synthesis. Then, a few of other types of COFs were Banerjee’s group reported an intramolecular
synthesized in the same method, all of them possessed oxidative biaryl synthesis based on Pd(II)@TpPa-1 in
great crystallinity and stability, indicating the 2014. In this work, more energy was put on the Heck
versatility of this method. In the catalytic performance reaction, Sonogashira reaction and a combined tandem
test, COF (TpAzo@Pd, Fig 9, Table 8) synthesized reaction catalyzed by Pd(0)@ TpPa-1 (Scheme 49, a,
through traditional solvothermal method was b, c).[74] Unfortunately, Pd NPs with broad size
compared with COF (HP-TpAzo@Pd) that distribution and aggregation of 20±10 nm were
synthesized in ILs. Interestingly, they both manifested observed. But this did not prevent the catalysts achieve
excellent catalytic ability in Suzuki reaction with small medium to great yields in Heck reaction and
size molecules. When it came to much larger size Sonogashira reaction. However, the recyclability
molecules, hierarchically porous HP-TpAzo@Pd still could not escape from the negative impact brought by
exhibited high activity (94%, Scheme 48) while ununiform NPs: an obvious deactivation was observed
reaction catalyzed by TpAzo@Pd only obtained a in the recycling tests: the catalytic activity decreased
small amount of product (12%). This result about 20%-30% after 4 cycles.
demonstrated that hierarchically porous make a
difference in the transport of large sized substrates and
products.
Scheme 48. Suzuki-Miyaura reaction with large-size Scheme 49. Sonogashira reaction (a), Heck reaction (b) and
substrates catalyzed by HP-TpAzo@Pd. cascade reaction (c) catalyzed by Pd(0)TpPa-1.
Last work we elaborated a new synthetic method of

COFs and compare it with the tradition one. In this
section, we are going to manifest the difference
between two metalation methods in various respects.
Actually, we have introduced these methods
previously, but no further investigation was performed
to figure out the potential reason: Ferdi and co-workers
found that Pt2+, which were immobilized into CTF in
or after the process of synthesis of CTF, displayed
different catalytic activities in the oxidation of Scheme 50. Heck coupling reaction catalyzed by Pd-trzn-
methane. In Ignacio’s work, Pd2+ were also COF (a) and Pd(II)X% BPy COF (b).
incorporated in to imine-linked COF in two ways, and
the following catalytic activities were evaluated
through Suzuki reaction. [97] In-situ metalation refers to The introduction of alkene to benzene generally
the metal precursors are added directly into reacting gives rise to inert substrate for next alkenylation due
COF polymer, and Gel metalation refers to the to the electron-withdrawing property of alkene.
addition after crystalline COFs are formed. After Vaidhyanathan and co-workers synthesized trzn-COF
32

(Fig 9, Table 8) to load Pd NPs and reaped great yields 4.3.2 Other coupling reactions
(up to 97 %) in multi-fold Heck coupling (Scheme 50,
a). [98] An interesting phenomenon was noticed in
loading process of Pd NPs: instead of using strong
reductants like NaBH4, the Pd2+ converted to Pd NPs
only through a simple stirring trzn-COF in ethanolic
solution of Pd2+ without any reductants. The author
assumed that the high content of N atoms in the
framework played a role in the reduction process.
Moreover, the contents of metals in one certain COF
were usually fixed, therefore, researchers choose to
change the amounts of COFs to evaluate the catalytic
activity in different dose of catalysts. Chai’s group
adopted the pore surface engineering strategy to adjust
the content of potential coordinate sites in 2016, thus
Accepted Manuscript
tuning the amount of metal catalysts in COFs.[99]
Pd(II)@X% BPy COFs (Fig 9, Table 8) all displayed
great catalytic performance in Heck reaction and
recycling tests (Scheme 50, b).
Scheme 52. The C-N coupling reactions catalyzed by

Cu/MCIP (a) and Cu@PI-COF (b).
Only few works reported other coupling reactions that

catalyzed by COFs. Kasi and co-workers reported a
partial crystalline triazine-based covalent imine
polymers (CIPs) as the support of Cu to catalyze Chan-
Lam cross-coupling reactions (Scheme 52, a, b).[102]
MCIP-1 and MCIP-2 (Fig 10, Table 9) was technically
Scheme 51. Asymmetric Henry reaction (a) and Heck COFs with only modest crystallinity, but they did
reaction (b) catalyzed by Pd@CCOF and COF-BTDH (c). showed great catalytic activity in such C-N coupling
reactions. In 2018, Zhang et al. a Cu immobilized
polyimide-based COF (PI-COF, Fig 10, Table 9) to
Organic chemists always emphasize the bulky catalyze the same reaction—coupling of aryl boronic
hinderance in chiral ligands, because they are the acids and amines (Scheme 52, c, d).[103] More than 80
insurance of high stereoselectivity and substrates were tested, from diverse substituted
enantioselectivity in chiral catalysis. The negative phenylboronic acids to various anilines, from benzene
impacts that those bulky ligands would bring to COFs to divergent heterocyclic compounds. All of them
were also elaborated in last chapter. But what if we can obtained good to excellent yields. A gram-scale
achieve excellent stereoselectivity and amplified experiment was also carried out and gained
enantioselectivity only with small-sized chiral groups, great yield, making Cu@PI-COF a great candidate to
they are so small that they will not cause any damage be used in industrial production.
to COFs. In 2017, Dong and co-workers introduced In 2019, Vaidhyanathan’s group developed a
chiral methyl groups and Pd NPs into COFs (CCOF- phenol-pyridyl-based COF to embed Cu/Cu2O NPs.
MPC, Fig 9, Table 8) to catalyze asymmetric Henry Such Cu@COF was utilized to catalyze Glaser-Hay
reaction and asymmetric reductive Heck reaction with coupling reactions chemoselectively (Scheme 53).[104]
nearly quantitative yields and excellent The medium yields of cross-coupling products—
enantioselectivity (Scheme 51, a, b).[100] However, unsymmetrical diynes generally felled into 60-80%.
large-sized substrates demonstrated inert activity due This was attributed to partial self-coupling products
to the reaction proceeded inside of the COF instead of and relatively low activity of large Cu/Cu2O NPs (2-3
simply on surface. Besides, although the catalytic nm). Thus, the author believed that further decrease in
activity of Pd NPs maintained after several recycling NPs (＜1 nm) would enhance the catalytic activity.
tests, aggregation of Pd NPs was still detected, which Further mechanistic studies verified its classic
then led to the decrease of crystallinity of CCOFs. catalytic cycle and pointed out that the interactions
Similarly, Ji et al. also established a COF (COF-BTDH, between NPs and COFs could modulate the redox
Fig 9, Table 8) recently to embed Pd NPs and catalyze activity and catalytic activity.
Heck reaction with high regioselectivity (Scheme 51,
c).[101] This work explored a wide substrate scope and
all reaped medium to great yields in low temperature,
but extra metallic additive Cu(OTf)2 was needed.
33

Scheme 53. Glaser-Hay coupling catalyzed by Cu@COF. comprise at least two consecutive reactions without
isolation of intermediate. Such process often makes a
difference in efficient synthesis of complex organic
We introduced Dong’s work in last section, which molecules. A classic example of cascade reaction is the
used small chiral methyl group to achieve high synthesis of tropinone developed by Robinson. With
enantioselectivity in Henry reaction and Heck the development of transition-metal catalysis, this
reaction.[100] Dong and co-workers continued to field received many attentions and was well developed.
explore in this area in 2019.[105] Generally, traditional The cascade reaction catalyzed by COFs is familiar to
reported thermal asymmetric catalysis was carried out us, we introduced few cascade reactions in the
at low temperature (-78 oC), which made high beginning of this review: the combination of
enantiomeric excess counterbalanced the low yields. deprotection reaction and condensation reaction
Interestingly, two photothermal conversion induced catalyzed by the COFs. In this part, the cascade
asymmetric reactions, asymmetric Henry reaction and reactions rely on multiple metals or on different
asymmetric A3-coupling reaction, were catalyzed by abilities of one simple metal.
Au/Pd NPs loaded homochiral COFs (CCOF-CuTPP, In 2015, Zhang et al. reported a Pd-loaded COF
Accepted Manuscript
Fig 10, Table 9) and obtained excellent yields (up to (COF-SDU1, Fig 10, Table 9) to catalyze the cross-
99 %) and high enantioselectivity (98 %) (Scheme 54). coupling reaction of silanes and aryl iodides (Scheme
The excellent catalytic performance was attributed to 55, a).[106] Pd(II)/COF-SDU1 was used to catalyze the
the synergy of CCOF confinement effect and M NP organosilane oxidation and following cross-coupling
catalytic activation. The structure of CCOF-CuTPP is reaction. A total yield of 96.5% was obtained in this
also interesting. We mentioned that porphyrin was cascade reaction. Traditional but classic methods, such
widely used in the establishment of COFs, this work as the introduction of triazine cores and imine linkages,
implanted Cu2+ into monomers and then constructed were still utilized in this work. Their extraordinary
the CCOF with chiral methyl group, which followed abilities to improve chemical stability of COFs and
by the load of Au/Pd NPs. CCOFs enabled these metal NPs worked. In the following year, Gao’s group
reactions to proceed either in xenon light or heat. reported two similar works: two bimetallic docked
Moderate yield (49%) and great stereoselectivity (96% COFs (Mn/Pd@Py-2,2'-BPyPh COF, RhI/PdII@75%
e.e.) were even obtained in nature sunlight irradiation. BPy COF, Fig 10, Table 9) were synthesized to
Another interesting thing is that various substrates catalyze two cascade reactions (Scheme 55, c, d).[107-
gave out different configuration in the A3-coupling 108]
The coordination models of two metals in two
reaction, both R and S configuration were gained in COFs were identical: the incorporation of bipyridine
excellent enantioselectivity (98 %). Moreover, further building blocks were used to dock Ru+/Mn2+ and imine
photothermal behaviour studies of linkages were used to embed Pd2+. But in the second
work, pore surface engineering strategy was used to
tune the contents of metal catalysts. Although both
works incorporated Pd2+, they served with different
functions. In the first cascade reaction, Pd2+ was used
to catalyze the Heck reaction, which was followed by
an epoxidation catalyzed by Mn2+; in the second one,
an addition of phenylboronic acid to benzaldehyde was
first catalyzed by Ru+, and Pd2+ was used to catalyze
the following oxidation of diphenylmethanol. Single
metal-docked COFs were also tested to catalyze the
Scheme 54. Asymmetric Henry reaction (a) and A3- cascade reaction in control experiments in both works,
coupling reaction (b) catalyzed by Au/Pd@CCOF. none of them could accomplish the entire process. This
result means the catalytic processes were mutual
independent.
these catalysts demonstrated that CCOFs not only
served as templates to take part in the construction of
chiral centers, but also functioned as photothermal
conversion materials. CCOFs enabled the easy light-
to-heat conversion and then initiated the reaction
through supplying abundant thermal energy. Anyway,
this work broke the bottleneck that the low yields
caused by thermal-induced asymmetric catalysis and
showed us a promising future for COFs to work as eco-
friendly and energy-saving catalysts. Scheme 55. Cascade reactions catalyzed by Pd(II)COF-
SDU1 (a), Mn/Pd@Py-2,2'-BPy-Ph COF (b) and RuI/PdII @
BPy COF.
4.4 Cascade reaction
Cascade reaction, also called domino reaction or
tandem reaction, refers to chemical processes that
34

In 2017, Banerjee and co-workers reported a Pd NPs asymmetric reactions.[113] For example, 4-V was used
loaded COF (TpBpy, Fig 10, Table 9) to catalyze a to catalyzed the cyanation of aldehydes with TMSCN,
cascade reaction (Scheme 56, a).[109] As we have 4-Co was used to catalyze asymmetric DA reaction, 4-
mentioned previously, the majority of metal NPs was Mn and 4-Fe were used to catalyze the epoxidation of
formed after the fabrication of COFs. This work, alkenes et al. (Scheme 57, b, c, d, e, f) It is worth
however, took a metal complex Bpy-PdCl2 as the mentioning that the imbedding of metal ions was
monomer to construct the Pd@TpBpy directly, which proceeded through substituting one metal ions to
also called “generates metal NPs in situ”. As the another according to the cation coordinating stability
cascade reaction was showed in Scheme 56 a, the with ligands in COFs. This means it is also possible to
yields only ranged from 26% to 80%. Besides, the incorporate more than two metal ions into one COF
relatively high temperature for this reaction led to and further catalyze tandem reactions. These are
slight agglomeration of NPs, which then gave rise to classic instances in the design of ligands into COFs,
the decrease of catalytic activity. In the same year, Ma the basic principles of turning ligands into building
et al. incorporated both pyridine monomers and Pd2+ blocks is same as the introduction of organocatalysts
into COFs (COF-TpPa-Py, Fig 10, Table 9). COF- into COFs: the maintaining of crystallinity of COFs.
Accepted Manuscript
TpPa-Py was used to catalyze an oxidation of alcohols Therefore, we are going to introduce another
followed by a Knoevenagel condensation reaction successful example in the following part.
(Scheme 56, b).[110] Similarly, Dong’s group embed Ru
NPs into COF (COF-ASB, Fig 10, Table 9) to
synthesize imines from benzyl alcohols and amines
without solvents (Scheme 56, c).[111] The optimal
reaction conditions for two steps in this cascade
reaction are mutually exclusive: the high temperature
for the oxidation step was unfavoured by the
condensation step. The introduction to COF, however,
made this possible and obtained total yields up to 93%.
Scheme 57. Organic reaction catalyzed by Lewis acid

catalysts in COFs.
Scheme 56. Cascade reaction catalyzed by Pd@TpBpy (a),
Pd/COF-TpPa-Py (b), Ru@COF-ASB (c).
4.5 Other reaction

Metal complexes possessing unoccupied orbital are
great Lewis acid catalysts for the activation of function
groups, such as carbonyl group. In this section,
researches were mainly expanded around the catalytic
ability of Lewis acid catalysts, such as the addition to
carbonyl group and ring open reaction of epoxides.
The Henry reaction we introduced in Dong’s work,[100]
for example, is a typical activation of carbonyl group.
In 2017, Wang’s group first designed salen ligands
into COFs (Fig 11, Table 10) to carry various metals,
including Cu2+, Ni2+, Zn2+, Co2+ and Mn2+.[112]
However, only Co/Salen-COF was testified for its
catalytic activity in Henry reaction (Scheme 57, a). At
the same time, Cui and co-workers also designed chiral
salen ligands into COFs (CCOFs, Fig 11, Table 10)
and imbedded various metal ions (Zn2+, Fe2+, Mn2+, Scheme 58. Various organic reaction catalyzed by Lewis
Co2+, Cr2+, V4+ and V5+) into them to catalyze diverse acid catalysts in COFs.
35

In 2016, Cui and co-workers designed chiral was formed through the condensation of (S)- or (R)-1-
TADDOL ligands derivatives into the building units of phenethylamine (PEA) and 1,3,5-
COFs (CCOF-1, CCOF-2, Fig 11, Table 10) to triformylphloroglucinol (Tp), such combination was
catalyze an asymmetric addition reaction with reversible and endowed the Tp molecule with the
Ti(OiPr)4 (Scheme 58, a).[114] The chiral dihydroxy memory to behave like a propeller conformationally.
groups of TADDOL played the major role in The author named this process as “chiral induction”.
asymmetric catalysis. One of the hydrogen atoms in Therefore, the following exchange with achiral
dihydroxy group took part in the formation of diamines would still lead to a torsion conformation, a
intramolecular hydrogen bond, and another one, on the
contrast, participated in the intermolecular interactions.
This strengthened the rigidity of the framework.
Dihydroxy groups are common coordinating sites in
various ligands. For example, Pascal et al. designed
derivatives of acac ligands into COF (acac-CTF, Fig
11, Table 10) to embed V5+, which was then used to
Accepted Manuscript
catalyze a modified Mannich reaction (Scheme 58,
b).[115] A plausible mechanism was also proposed
according previous researches (Scheme 59, a). More
importantly, the homogeneous counterpart, VO(acac)2,
was inert for some substrates, such as 1-naphthol and Scheme 59. Two examples of proposed mechanism of
phenol. But V@acac-CTF remained high catalytic reactions catalyzed by Lewis acid catalysts in COFs.
activities for these substrates, which implies the
combination of COFs with metal ions further enhanced
the catalytic activity of metal ions. Similarly, Ma and conformation that is similar with axially chiral
co-workers also immobilized VO2+ into bishydroxyl- compound, instead of a C3-symmetric one. Nine
based-COF (TAPT-2,3-DHTA COF, Fig 11, Table 10) propeller-like chiral COFs were synthesized through
to catalyze a Prins-type cyclization reaction and chiral induction strategy, they could be used in
sulfide oxidation reaction (Scheme 58, c).[77] Not enantioselective sensing of saccharides owing to their
surprisingly, the COF-supported VO2+ still showed high fluorescence. The enaminone groups in one of the
much higher catalytic activity than its homogeneous CCOF could be anchoring sites to coordinate with
counterparts, such as VO(acac)2 and VO(catechol)2. Cu2+ to form CCOF-TpTab-Cu, which was then
Besides, the potential mechanisms of two reactions utilized to catalyze asymmetric Henry reaction
were also put forward (Scheme 59, b). In the same year, (Scheme 60). Although a low enantioselectivity (31%
Zhao’s group introduced dihydroxy groups, which e.e.) was obtained, it did match the speculation due to
served as the anchoring sites of Co2+, into hydrazine- the chirality of CCOFs came from stereo-hinderance
based COFs (NUS-50, NUS-51, Fig 11, Table 10) to of propeller-like conformation, instead of typically
catalyze the silylation of benzaldehyde reaction effective chiral active sites. Therefore, further studies
(Scheme 58, d) with excellent yields (up to 98 %).[116] are still needed to elevate the enantioselectivity and
A COF with similar structure and two ethoxy groups catalytic application in other reactions.
was also synthesized and coordinated with Co2+, but
exhibited not catalytic activity in this reaction. This
result further verified the importance of choosing
anchoring sites. The usability of defect sites was
elaborated in former works, Tang and co-workers took
this strategy to create defective sites in COFs (LZU-
Scheme 60. Asymmetric Henry reaction catalyzed by
OH, Fig 11, Table 10) through metalation with
CCOF-TpTab-Cu.
Fe3+.[117] The catechol-type building units are great
coordinating sites for metals owing to its strong
chelating ability, the counterparts are often used in
homogeneous organic catalysis. Therefore, the Few examples were developed to construct the C-O
catalytic performance of metal-loaded LZU-OFe was bond so far, Pieter and co-workers first established a
verified through the alcoholysis of epoxides (Scheme phosphine-based COF (Pd(acac)2/COF, Fig 11, Table
58, e), and excellent yields (up to 99 %) of the products 10) to load Pd2+ and thereby catalyzing telomerisation
were obtained. of 1,3-butadiene with phenol and glycerol (Scheme
We have demonstrated two methods to construct 61).[119] Interestingly, this reaction was carried out
chiral COFs (CCOFs): the attachment of chiral groups without any solvents and additives. Besides, the
to the pore walls or knots; the direct design of chiral selectivity could be tuned through adjusting the P/Pd
molecules into the building blocks of COFs. In 2018, rations in COFs. However, the reaction with glycerol
Cui and co-workers developed the third method in the still suffered with poor conversion and selectivity.
construction of CCOFs: the “chiral induction” Moreover, the Pd in COFs suffered from leaching
strategy.[118] The monomers in this strategy are all problems. Therefore, investigation of COFs in the
achiral ones. A propeller geometry chiral precursor catalytic construction of C-O bonds are still needed.
36

Scheme 61. The construction of C-O catalyzed by

Pd(acac)2/COF.
Accepted Manuscript
37

Accepted Manuscript
Fig 8. Structures of (Pd/Au)/COF, (Pd)@CTF, TAPB-DMTP-COF, COF-AO, Thio-COF, TFPPy-PyTTA COF, DBA-2D-COF,
and TFP-DAQ COF.

Table 7. A summary of structure data of relating COFs in reduction reaction

COF TGA ( °C) Ref.
(m2g-1) (nm) (cm3g-1)
TAPB-DMTP-COF 400 2422 3.24 [80]
Au/TAPB-DMTP-COF 400 2411 3.24 [80]
Fe3O4@ COF-Au 250 193.44 [81]
CuFe2O4/Ag@COF 300 464.21 3.15 0.396 [82]
Thio-COF 300 50 2.4 [83]
(Pd/Au)/COF 300 577 4.2 0.35 [84]
Pd/COF 555 4.2 0.22 [84]
Au/ COF 560 4.2 0.23 [84]
(Pd)@CTF 55 [85]
Pd@CTF 39 [85]
TFPPy-PyTTA COF 230 1120 1.7 1.14 [88]
Co2+@TFPPy-PyTTA
Accepted Manuscript
230 600 1.2 0.84 [88]
COF
Zn(II)@TFP-DAQ COF 1117.375 3.5 1.31 [89]
COF-AO 280 397.11 2.08 [90]
Pd@COF-AO 347.41 1.36 [90]
DBA-COF 5 430 1643 1.9 0.70 [91]
Ni-DBA-2D-COF 1565 1.8 0.68 [91]

Accepted Manuscript
Fig 9. Structures of COF-LZU1, H2P-Bph-COF, Phos-COF-1, HP-TpAzo, COF-300, TAT-TFP, TAPB-BTCA, BPyCPF,
CCOF-MPC, trzn-COF and COF-BTDH.

Table 8. A summary of structure data of relating COFs in coupling reaction.

BET Surface Area Pore volume
COF TGA ( °C) Average Pore size (nm) Ref.
(m2g-1) (cm3g-1)
COF-LZU1 310 410 1.2 0.54 [15]
Pd/COF-LZU1 270 146 1.2 0.19 [15]
H2P-Bph-COF 400 550 1.69, 2.92 0.53 [92]
Pd/ H2P-Bph-COF 150 147 1.68, 2.92 0.39 [92]
COF-300 1373 [93]
Pd(OAc)2@COF-
270 [93]
300
TAT-TFP 400 646 1.17 0.36 [94]
Pd(II)/ TAT-TFP 140 292.0 0.145 [94]
Pd(0)/ TAT-TFP 140 52.2 0.094 [94]
Phos-COF-1 400 818 1.56 [95]
HP-TpAzo 350 179 5-13 [96]
Accepted Manuscript
TAPB-BTCA 888 1.52 [97]
Pd@ TAPB-BTCA
494 1.52 [97]
in-situ
TAPB-TFP 550 [97]
Pd@ TAPB-TFP
664 [97]
in-situ
trzn-COF 350 408.5 2.3 [98]
Pd- trzn-COF 140 404 1.9 [98]
25% BPy COF 280 538 2.6, 2.7 [99]
Pd@25% BPy COF 283 2.3 [99]
75% BPy COF 280 1438 2.6, 2.7 [99]
Pd@75% BPy COF 847 2.1 [99]
CCOF-MPC 350 101 0.41 0.10 [100]
Pd@CCOF-MPC 686 1.26 0.33 [100]
COF-BTDH 580 91.6 2-3 0.28 [101]
Pd/ COF-BTDH 150 65.6 2-3 0.13 [101]
Table 9. A summary of relating structure data of COFs in coupling reaction.

COF TGA ( °C) Ref.
(m2g-1) (nm) (cm3g-1)
MCIP-1 300 174 3.24 [102]
Cu/MCIP-1 200 [102]
MCIP-2 300 187 4.43 [102]
PI-COF 401 [103]
Cu@ PI-COF 297 [103]
IISERP-COF9 350 1172 1.3 [104]
CCOF-CuTPP 350 686 1.25 [105]
Au@ CCOF-CuTPP 95 0.73 [105]
Pd@ CCOF-CuTPP 101 0.81 [105]
COF-SDU1 450 1125 2.63 1.20 [106]
Pd(II)/ COF-SDU1 250 1052 2.51 1.16 [106]
25% BPy COF 500 538 3.77 0.53 [106]
50% BPy COF 500 1554 3.76 1.26 [106]
75% BPy COF 500 1438 3.74 1.11 [106]
100% BPy COF 500 1288 3.73 0.98 [106]
Py-2,2'-BPyPh COF 500 2038 2.6 1.829 [106]
Mn@Py-2,2'-BPyPh
1711 2.6 1.708 [106]
COF
Mn/Pd@Py-2,2'-
1562 2.0 1.654 [106]
BPyPh COF
PdII@25% BPy COF 283 3.71 0.30 [107]
PdII@50% BPy COF 982 3.70 0.59 [107]
PdII@75% BPy COF 847 3.68 0.53 [107]
PdII@100% BPy
731 3.65 0.45 [107]
COF
41

RuI/PdII@25% BPy
115 3.74 0.23 [107]
COF
RuI/PdII@50% BPy
146 3.71 0.26 [107]
COF
RuI/PdII@75% BPy
97 3.68 0.19 [107]
COF
TpBpy 350 1462 2.3 [108]
Pd@TpBpy 350 653 1.4-2.3 [108]
COF-TpPa-Py 400 1019 1.5 0.56 [109]
Pd/COF-TpPa-Py 902 1.3, 1.5 [109]
COF-ASB 350 233.15 2.5 [110]
Ru@COF-ASB 101.92 2.0 [110]
Table 10. A summary of structure data of relating COFs in cascade reactions and other reactions.
COF TGA (°C) Ref.
Accepted Manuscript
(m2g-1) (nm) (cm3g-1)
Salen-COF 344 1366 2.5 0.73 [112]
Co/Salen-COF 854 2.5 [112]
CCOF 3 350 826 1.84 0.61 [113]
CCOF 4 350 683 1.65 0.45 [113]
CCOF 4-Mn 614 1.66 [113]
CCOF 4-V 547 1.66 [113]
CCOF 4-Co 628 1.63 [113]
CCOF 4-Fe 586 1.70 [113]
CCOF 4-Cr 633 1.73 [113]
CCOF 4-Cr-Mn 616 1.67 [113]
CCOF 4-Cr-Co 585 1.59 [113]
CCOF 4-Cr-Fe 554 1.66 [113]
CCOF-1 380 266 1.02 0.32 [114]
CCOF-2 380 335 1.06 0.51 [114]
acac-CTF-5-400 500 1131 0.90 [115]
acac-CTF-10-400 500 1150 0.95 [115]
acac-CTF-5-500 500 1556 1.20 [115]
acac-CTF-10-500 500 1626 1.60 [115]
TAPT-2,3-DHTA
400 1151 3.0 [77]
COF
VO-TAPT-2,3-
400 562 2.5 [77]
DHTA COF
NUS-50 350 520 2.5 [116]
NUS-50-Co 102 [116]
NUS-51 350 510 2.5 [116]
LZU-OH 473 1.2, 0.59, 0.81 [117]
LZU-OFe 400 122 1.2 [117]
CCOF-TpPa-1 350 832.4 1.1-2.51 [118]
CCOF-TpPa-2 350 1077.4 1.1-2.51 [118]
CCOF-TpPa-Py 350 1178.1 1.1-2.51 [118]
CCOF-TpBD 350 849.3 1.1-2.51 [118]
CCOF-TpPa-Me2 350 878.1 1.1-2.51 [118]
CCOF-TpPa-OMe2 350 602.8 1.1-2.51 [118]
CCOF-TpBpy 350 1073.4 1.1-2.51 [118]
CCOF-TpTd 350 1217.8 1.1-2.51 [118]
CCOF-TpTab 350 482.6 1.1-2.51 [118]
(Pd(acac)2)/COF 380 135 0.04 [119]
42

Accepted Manuscript
Fig 10. Structures of trzn-COF, PI-COF, COF-TpPa-Py, IISERP-COF9, COF-CuTPP, BPy COF, TpBpy COF and COF-ASB.

Accepted Manuscript

Accepted Manuscript
Fig 11. Structures of M/Salen-COF, CCOF-4, CCOF-1/2, acac-CTF, TAPA-2,3-DHTA COF, NUS-50, Pd(acac)2/COF, LZU-
OH, CCOF-Tab, and various CCOFs.

5. Relatives of COFs in catalytic organic

catalysis
There are other porous organic polymers (POPs) that
possess similar structures with COFs, such as
hypercrosslinked polymers (HCPs),[120] porous aromatic
frameworks (PAFs),[121] conjugated microporous
polymers (CMPs)[122] et al. These organic polymers are
Scheme 62. Suzuki-Miyaura coupling reaction (a) and
not mutually exclusive, which means there are no clear
bromination reaction (b) catalyzed by HCPs.
boundaries among them. But these organic polymers
have their own merits: the high chemical stability
endowed by irreversible chemical bonds, the crosslinked
network of HCPs, the record-high surface area and
Accepted Manuscript
porosity of PAFs, the extended π-conjugation network of
CMPs and so on. The most distinct character of COFs,
undoubtedly, is their high crystallinity owing to dynamic
covalent chemistry. On the contrast, the most common
trait of these organic polymers is the diversity of organic
building blocks. Besides, organic polymers are
heterogeneous, this makes all of them potential
candidates for heterogeneous organic catalysis.
Therefore, few examples and their catalytic performance
will be briefly introduced in this part.
5.1 HCPs in catalytic organic synthesis

Fig 12. Structures of KPAs(Ph)-PPh3 and KPAs(Ph-PPh3).
The crosslinked networks of HCPs are generally Reproduced with permission. Copyright 2012, Wiley-VCH.
formed through Friedel-Crafts reaction, a simple but
versatile synthetic approach to construct porous organic
materials. In 2012, Li and co-workers established
microporous knitting aryl PPh3-based network polymers
(KPAs(Ph)-PPh3, KPAs(Ph-PPh3), Fig 11) to serve as the
support of Pd2+. The catalytic performance was evaluated
through Suzuki-Miyaura coupling reactions under mild
conditions (80 oC, aqueous ethanol solution, Scheme 62,
a).[123] The former introduced Suzuki reaction catalyzed
by COFs usually only worked for aryl bromides and aryl
iodide. Aryl chlorides, however, are generally inert for
this reaction. This work filled this blank as heterogeneous
catalysts. Moreover, control experiments relating to the Scheme 63. visible-light induced bromination reaction
recycling, leaching and aggregation problems were catalyzed by HCPs.
carried out. The HCPs materials performed well in these
experiments. In 2016, Zhang et al. reported a selective
visible-light induced bromination reaction catalyzed by a 5.2 PAFs in organic catalysis
series of microporous organic polymers (MOPs) with
crosslinked networks (Scheme 62, b).[124] By adding KI
as hole scavenger and CuCl2 as electron scavenger, the
author confirmed that the importance of photogenerated
species in the mechanism (Scheme 63). According to
previous reports, oxygen trapping agents, DMPO and
TEMP were utilized to further verify the proposed
mechanism. The MOPs worked as the same role as
compared to the photoinduced reactions catalyzed by
COFs.
Scheme 64. Cascade reaction (a) and oxidation reaction (b, c)
catalyzed by PAFs.
46

The 3D disordered frameworks of PAFs are great first incorporated Fe3+-coordinated porphyrin into CMPs
heterogenous catalysts owing to their tremendous BET (Fig 14) to catalyze selective oxidation of thioanisole
surface area (more than 5000 m2g-1) and robust stability (Scheme 65, a). [127] A gram-scale (8.3 g) experiment was
endowed by irreversible C-C bonds. Because they are carried out and high TON (97320) was achieved after
energetically stable and favored by atomistic simulation. thorough screen of conditions. In 2013, Andrew’s group
In 2016, Feĺix’s group developed an Ru-loaded PAF designed rose bengal dye molecule into CMPs through
(PAF-NProRh, Fig 13) to catalyze a cascade reaction. Sonogashira cross-coupling polycondensation reaction.
Knoevenagel condensation and following hydrogenation Rose Bengal dye molecule is an organic photosensitizer,
reaction were catalyzed by PAF-NproRh with great which made the CMPs(Fig 13) great photocatalysts to
yields (up to 97 %) (Scheme 64, a).[125] Just as how COFs catalyze visible-light-induced Aza-Henry reaction
functioned in “COFs themselves as catalysts part”. In this (Scheme 65, c).[128] Only a small loss in the catalytic
case, prolinamide groups were introduced to coordinate activity was observed after ten cycles, proving the great
with Ru2+ and served as base sites to catalyze the cascade recyclability of CMPs. In the same year, Deng et al.
reaction. No significant loss of catalytic activity was reported a Salen-based and Co/Al-coordinated CMPs
observed in the recycling tests for 10 circles. In 2018, Ji (Fig 14) to catalyze the fixation of CO2(Scheme 65, b).
[129]
and co-workers incorporated an Sn-coordinated The CMPs in this work were great CO2 capture
Accepted Manuscript
porphyrin into PAF (SnPor@PAF, Fig 13) to catalyze materials because of their excellent adsorption capacity.
visible-light-driven selective oxidation of thioanisole and However, the catalytic performance dropped quickly
oxidative coupling reaction of primary amines (Scheme after recycles in mild condition (25 oC, 0.1 MPa CO2), a
64, b, c).[126] As we have introduced, the metal- much harsh condition (100 oC, 3.0 MPa CO2) was needed
coordinated porphyrin has great potential for to counterbalance the decreased catalytic activity of
photocatalytic reaction not only in COF, but also in other CMPs for the purpose of recovering the yields.
POPs.
Fig 13. Structures of PAF-NProRh and SnPor@PAF. Fig 14. Structures of FeP-CMP, Al/Co-CMP and RB-CMP1.
5.3 CMPs in organic catalysis 6. Conclusions and Outlooks

In this review, we established a simple system to classify
the organic reaction that had been transplanted into
COFs: from COFs themselves as catalysts to metal/non-
metal complexes-based catalysis. We use diverse
classification methods in each chapter, it is vital to
declare that these methods are not mutually exclusive.
For instance, we are able to classify any organic reaction
through their reaction mechanism, just like what we did
in the fourth chapter. And we can also classify them
through the synthetic methods of COFs, just like “bottom
up” strategy and post-modification strategy. We hope
Scheme 65. The oxidation of thioanisole (a), fixation of CO2 that this could present diverse perspectives by utilizing
(b) and Aza-Henry reaction (c) catalyzed by CMPs. different classification methods in different chapter.
Moreover, from works we aforementioned, we can figure
out that COFs have begun to make a name for themselves
As we can see from the term “Conjugated Microporous in organic synthesis. Although imines-linked COFs and
Polymers”, many COFs could also be termed as CMPs. CTFs are great potential candidates for catalysis owing to
Because many conjugated linkages, such as imine-typed their high stability, new issues are still rising. In this
linkage, were developed. In 2010, Jiang and co-workers
47

Fig 15. Structures of some common building blocks used in COFs.
Accepted Manuscript
chapter, we are going to discuss some intractable exploring for new synthetic methods and building blocks,
problems and promising solutions in multiple respects. the work established by Wang’s group to add “latches”
on the linkage, for example, is a great example to
strenghen the stability of COFs.[48]
6.1 Synthesis The general method for the exploration of real
structures of COFs remain limited. Given the nature of
Starting from the synthetic conditions, the bulk of COFs organic polymers, even those COFs with modest or high
used in catalysis are prepared through solvothermal crystallinity can only yield powder crystals rather than
synthesis. The process of self-correction needs certain single crystals. This prevents them from using the most
synthetic conditions to ensure the crystallinity of COFs. precise method for structure analysis—single crystal X-
In early stage, it sometimes took chemists long times to ray diffraction. On the contrast, we always use powder
find out the optimal conditions to achieve the X-ray diffraction (PXRD) to get data relating to the
thermodynamic equilibrium. Therefore, it not an easy structures and then match them with simulating ones to
thing to obtain agreeable synthetic conditions. Moreover, judge the similarity. However, this method is unavailable
the synthesis of COFs is always carried out under harsh when it comes to 3D COFs due to their complexity. Of
conditions (inert environment, toxic solvent, high course, efforts have been made and COF-300, COF-320,
temperatures et al.). Long time, low yields and small LZU-79 et al. were reported as single crystals through
scale are also tough task that need solutions. In this case, carefully chosen of solvents to control the nucleation
various synthetic methods, such as microwave synthesis, process.[131-133] Moreover, the complicated structures of
ionothermal synthesis and mechanochermical synthesis 3D COFs were also determined through more
were explored to solve these problems successfully. TPT- sophisticated methods, such as 3D rotation electron
COF-1, for example, was synthesized in a gram scale, but diffraction (RED) reported by Yaghi’s group in 2013.[132]
the universality still needs further study.[130] However, these methods require great efforts and
expensive machines, a much general method is still
highly desired. The reason is that they are crucial for
6.2 Structures further study of reaction mechanism. The understanding
of the conversion of substrates in the pores of COFs will
It is true that COFs are famous for their diversity, but the help us solve the scaling effect in amplification process.
majority of COFs utilized in organic catalysis were still
imine-linked COFs owing to their stability. However,
these COFs are not invincible, many of them lost partial 6.3 Catalysis
or even entire catalytic activity after several recycles. For
example, the extensive exposure to visible light in light- Great improvements were made by COFs for
induced reactions. Besides, COFs or metals in COFs still heterogeneous catalysis in organic synthesis in last
suffer from the damage caused by high temperature, decade. Many advanced reactions in modern organic
since metal NPs will aggregate in thermal conditions. chemistry were successfully accomplished by COFs,
From the instance above mentioned, it is not difficult to such as transition-metal catalyzed cross-coupling
find out the significance of stability of COFs in catalysis. reactions and visible-light-induced organic reactions.
Moreover, harsh conditions are not only used in the Apart from that, COFs also exhibit great potential in the
synthesis of COFs, but are also utilized in the catalytic catalysis of fundamental but vital organic reactions, such
process. Except from that, Ma and co-workers also made as Knoevenagel condensation reactions, Diels-Alder
COFs become shields for enzymes to prevent them from reaction, asymmetric Michael addition reaction et al.
further deactivation. This also heavily relies on the However, given the wide range of organic reactions and
chemical stability of COFs.[28] Therefore, we cannot stop those hot topics, many frontiers are still waiting for

exploration. The functionalization of inert C(sp3) −H [10]S. Zhao, B. Dong, R. Ge, C. Wang, X. Song, W. Ma,
bonds and the construction of complex chiral centers, for Y. Wang, C. Hao, X. Guo, Y. Gao, RSC Adv. 2016,
example. Except from the types of organic reactions, the 6, 38774-38781.
harsh catalytic conditions, the limited scope of reaction
substrates and the reusability still need improve. [11]X. Ding, J. Guo, X. Feng, Y. Honsho, J. Guo, S. Seki,
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Conflicts of interest Nakamura, S. Irle, S. Fukuzumi, A. Nagai, D. Jiang,
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There are no conflicts of interest to declare.
[13]S. Wan, J. Guo, J. Kim, H. Ihee, D. Jiang, Angew.
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53

REVIEW
Covalent Organic Frameworks in Catalytic Organic
Synthesis
Adv. Synth. Catal. Year, Volume, Page – Page
Hai-Yang Cheng, Tao Wang*
Accepted Manuscript
54

COF Catalysis

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COF Catalysis

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Title: Covalent Organic Frameworks in Catalytic Organic Synthesis

Authors: Haiyang Cheng and Tao Wang

To be cited as: Adv. Synth. Catal. 10.1002/adsc.202001086

Link to VoR: https://doi.org/10.1002/adsc.202001086

Covalent Organic Frameworks in Catalytic Organic Synthesis

Received: ((will be filled in by the editorial staff))

1 Introduction equilibrium was built upon dynamic covalent

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the embryos of diverse n-type, p-type and ambipolar-

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quickly after several recycles. This result implies the

Scheme 4. Knoevenagel condensation reaction catalyzed

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2,3- intermediary agents to help energy transfer from

Scheme 6. Diels-Alder reaction catalyzed by Py-An COF (a)

Jiang and co-workers first introduced COFs (Py-An

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molecular oxygen rather than water. Plausible

The CDC reaction, arylation reaction mentioned above

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This speculation was further validated by time-resolved

Scheme 13. Dehalogenation reaction (a, c), α-alkylation of

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searching for COFs with excellent stability will always

As we all know, building chiral centers is always tough

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Scheme 19. Proposed mechanism of asymmetric α-alkylation

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Por-sp2c-COF 250 689 1.85 1.75 [49]

Table 3. CO2 fixation reaction catalyzed by COFs.

other gases, such as methane, nitrogen or carbon

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3. As supports of non-metal complexes

3.1 “Post-modification” Strategy

Scheme 23. Diels-Alder Reaction catalyzed by BF3 ⊂COF-701.

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Fig 5. Structures of CTF-1/P, CTF-CSU1/19, CCTF, COF-JLU6/7, COF-IL, OMe-OH-TPBP-COF, OH-TPBP-COF.

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introduces us the importance of choosing “platform

Actually, we have introduced this method in last chapter:

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3.3 As supports of linear polymers.

Scheme 26. α-Aminooxylation of aldehydes (a) and aldol

Scheme 27. Asymmetric Steglich rearrangement (a) and

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racemic 1-phenylethanol reaction catalyzed by lipase@COF-

If it remains tough to create stable man-made analogue

Scheme 31. (a) Schematic illustration of the translocation of

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Table 5. A summary of structure data of relating COFs as supports of non-metal complexes

BET Surface Area Average Pore size Pore volume

4 As Supports of Metal Complexes immobilizing metal complexes to various materials like

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Ru/CTFs (Fig 7, Table 6) were utilized by Palkovits and