Thiophene-embedded conjugated microporous polymers for photocatalysis

Article abstract of DOI:10.1039/d0cy01164a

Various photoactive building blocks can be incorporated into porous organic polymers (POPs). The intrinsic properties, such as various synthetic methods, outstanding inherent porosity, easy tunability, rigid conjugated skeletons and high stability, endow the polymeric organic networks with wonderful potential to act as heterogeneous photocatalytic platforms. However, exploitation of efficient synthetic strategies for metal-free and nontoxic heterogenous photocatalysts, and further insights into the photocatalytic process in organic transformations are still necessary. In this context, we report the concise synthesis of two polymeric frameworks (BTP-CMP and TBTP-CMP) incorporated into bithiophene and thiophthene units via a "bottom-up"strategy. BTP-CMP and TBTP-CMP were employed as heterogeneous photocatalysts in the synthesis of benzimidazoles, and exhibited excellent catalytic activity (up to 98% yield, at least 15 iterative runs). Therefore, the thiophene-embedded networks can serve as stable efficient and recyclable heterogeneous photocatalysts. Additionally, based on the catalytic results of control experiments and the energy band structures of the materials and intermediates, a possible photocatalytic reaction mechanism has been proposed.

Full text of DOI:10.1039/d0cy01164a

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Y. Du, S. Ding, Z. Li, S. Jiang, Y. Qin, X. Liu, P. Wei, Z. Cao, M. Song and Z. Pan, Catal. Sci. Technol., 2020,
DOI: 10.1039/D0CY01164A.
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ISSN 2044-4761
PAPER
Chaoqiu Chen, Yong Qin et al.
Highly dispersed Pt nanoparticles supported on carbon
nanotubes produced by atomic layer deposition for hydrogen
generation from hydrolysis of ammonia borane
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Page 1 of 10
CP al et aa lsy es i ds oS c ni eo nt c ae d &j uTs et c mh na or gl oi ng sy
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DOI: 10.1039/D0CY01164A
ARTICLE
Thiophene-embedded Conjugated Microporous Polymers for
Photocatalysis
a
a
a
b
c
a
a
Wan-Kai An,* Shi-Jia Zheng, Ya-Nan Du, San-Yuan Ding,* Zhi-Jun Li, Song Jiang, Yuchen Qin,
a
d
a
a
a
Xiaobiao Liu, Pi-Feng Wei, Zhan-Qi Cao, Meirong Song, and Zhenliang Pan*
Received 00th January 20xx,
Accepted 00th January 20xx
Various photoactive building blocks can be incorporated into porous organic polymers (POPs). The congenital properties,
such as various synthetic methods, outstanding inherent porosity, easy tunability, rigid conjugated skeletons and high
stability, endow the polymeric organic networks with wonderful potential to act as heterogeneous photocatalytic platforms.
Whereas, exploiting efficient synthetic strategies for metal-free and nontoxic heterogenous photocatalysts, and further
insight into the photocatalytic process in organic transformation are still necessary. In this context, we report the concise
synthesis of two polymeric frameworks (BTP-CMP and TBTP-CMP) incorporated bithiophene and thiophthene units via a
DOI: 10.1039/x0xx00000x
“bottom-up” strategy. BTP-CMP and TBTP-CMP were employed as heterogeneous photocatalysts in the synthesis of
benzimidazoles, and exhibited excellent catalytic activity (up to 98% yield, at least 15 iterative runs). Therefore, the
thiophene-embedded networks can serve as stable efficient and recyclable heterogeneous photocatalysts. Additionally,
based on the catalytic results of control experiments and energy band structures of materials and intermediates, the possible
photocatalytic reaction mechanism has been proposed.
solution to the issues is to exploit efficient, stable, cost-effective,
metal-free and nontoxic heterogenous photocatalysts which are
recyclable and reusable.8
Porous organic polymers (POPs) have recently emerged as
excellent platforms to assemble structural building blocks (SBBs) and
Introduction
More recently, exploiting greener and concise synthetic methods to
high value-added fine chemicals has become the common pursuit in
1
labs and chemical industries. As a clean energy source, sunlight is
9
functional building blocks (FBBs) via strong covalent linkages.
essential for numerous of life process on the earth, e.g. natural
1
0
2
Represented by conjugated microporous polymers (CMPs) and
covalent organic frameworks (COFs)9h, 9j, 11 etc., POPs have been
widely used in photoelectricity,12 molecular recognition/sensors,13
gas adsorption/separation/storage,14 membrane separation,15
energy storage,16 pollutants elimination,17 drug delivery,18 and
heterogeneous catalysis.8a, 19-21 Benefiting from the various synthesis
methods and easy tunability for POPs, numbers of versatile porous
photosynthesis. In the meanwhile, many of the key intermediates
(i.e. radicals, radical ions and ions) that will further fabricate
complicated functional molecules can be generated in situ under
illumination.3 Driven by photocatalysts under light radiation,
photocatalysis, a powerful synthetic technique which offers a viable
solution for traditional organic transformations and energy issues.
2
The classical photocatalysts are mainly metal oxides/suifides (TiO ,
2
2, 21e
4
5
organic catalysts that with photocatalytic
or asymmetric
showcase wonderful potential in the
CdS, ZnS etc.), polyoxometalates, organic noble-metal complexes
catalytic activity8b,
23
etc, bpy = bipyridine, ppy = 2-phenylpyridine]6
[
Ru(bpy) Cl , Ir(ppy)
3 2 3
and organic dyes (Eosin Y, Rose Bengal, methylene blue etc).7
preparation of fine chemicals. The pure organic skeleton enable POPs
could enrich organic guest molecules inside pores, and thus improve
the relative concentration of reactants. Besides, the photoactive
units and rigid π-π conjugated skeletons can assist POPs to harvest
photon and transfer electron.22j, 24 The congenital advantages above
render POPs can be served as photocatalysts carrier to induce the
produce of intermediates and promote organic transformation
under mild lighting conditions. Furthermore, these solid catalysts
undoubtedly simplify the purification procedures and enhance the
utilizability of homogeneous catalysts.
The structural uniqueness of thiophene (TP) has brought TP-
embedded molecules with various dimensions great potential for
practical applications. In this aspect, diverse POPs that contain TP
units (TP-POP) have been synthesized through C-C coupling, C-H
activation, cyclotrimerization of cyano group, and imine linkage.25
However, most catalysts above are costly or highly toxic, even suffer
from the limited visible-light absorption, high catalyst loading, poor
efficiency and unable to achieve applications in large scale.4-7 In
addition, it is not easy to separate the homogeneous catalysts from
reaction systems and then reuse them. In consequence, a practicable
aCollege of Science, Henan Agricultural University, Zhengzhou, Henan 450002, China.
E-mail: anwk@henau.edu.cn, panzhenliang@sina.com.
b
State Key Laboratory of Applied Organic Chemistry, College of Chemistry and
Chemical Engineering, Lanzhou University, Lanzhou,Gansu 730000, China. E-mail:
dingsy@lzu.edu.cn
c
College of Chemistry and Chemical Engineering, Longdong University, Qingyang,
Gansu 745000, China.
School of Chemistry & Chemical Engineering, Linyi University, Linyi, Shandong
76000, China.
Electronic Supplementary Information (ESI) available: Synthesis of Monomers and
d
2
†
TP-CMPs, SEM, TEM, TGA, PXRD, EDS and CV of TP-CMPs, FT-IR spectra of the fresh
and recycled catalyst, recyclability test of BTP-CMP, and NMR spectra of products.
See DOI: 10.1039/x0xx00000x.
Several of the reported POP examples are mainly focused on the
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ARTICLE
Journal Name
Experimental
View Article Online
DOI: 10.1039/D0CY01164A
General materials and methods
,5-dibromothieno[3,2-b]thiophene
tris(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzene
2
(TBTP-2Br)
and
1,3,5-
(TTDB)
were prepared according to the literature procedures (see the
ESI†).12c, 28 Other reagents, e.g. 5,5'-dibromo-2,2'-bithiophene (BTP-
2
Br), could be purchased from commercial suppliers (Energy
Chemical Reagent Co. Ltd and Adamas Reagent Co. Ltd) used without
further purification, unless otherwise noted. All Pd-mediated
coupling reactions were first degassed and then carried out under Ar.
Liquid NMR spectra ( H and 13C) were recorded on a Bruker Avance
1
III 400 MHz NMR spectrometer (CDCl
state NMR experiments were performed on a Bruker WB Avance II
00 MHz NMR spectrometer (4-mm double-resonance probe):
3 6
or d -DMSO as solvent). Solid-
4
contact time was 3 ms (ramp 100), recycle delay was 2 s and the
spinning rate was 10,000 ± 1 Hz. FT-IR spectra were obtained with a
Nicolet IS-20 instrument. Nitrogen adsorption and desorption
Scheme 1 Schematic representation for the synthesis of thiophene- isotherms were measured at 77 K using a Micromeritics ASAP 2020M
based CMPs (TP-CMPs). Reagents and conditions: BTP-2Br or TBTP- system. Thermogravimetric analysis (TGA) were carried out on a SDT
2
Br, TTDB, Pd(PPh
3 4
) , 2 M K
2
CO
3
, N, N-dimethylformamide (DMF), Q600 (V20.9 Build 20) instrument from 35 °C to 1000 °C (10 °C/min)
under a nitrogen atmosphere. Scanning electron microscope (SEM)
o
Ar, 150 C, 2 days.
tests were used to examine the surface morphologies and
microstructures of materials with Zeiss GeminiSEM 500 at a voltage
of 15.0 kV. Elemental compositions within the porous networks were
applications in adsorption for iodine26 or carbon dioxide,25j, 25k
lithium-ion batteries.27 However, very few TP-POP catalysts have
been reported so far, especially those cases of their catalytic
activities derive from TP units.25a-g, 25m Moreover, the excellent
photoelectric properties demonstrate that TP-POPs might work as
photocatalysts. For example, instructive works by Zhang et al. have
confirmed the significant photocatalytic activities of TP-based POPs
in organic transformation when incorporate with strong electron
acceptor, i.e. triazine or benzothiadiazole.25e-g Besides, Liu group and
Thomas group realized the photocatalysis of hydrogen production
analysed by mapping experiments. High resolution transmission
electron microscopy (HR-TEM) images were acquired by a Tecnai G2
F30 TEM operating at an acceleration voltage of 300 kV. UV-Vis
diffuse reflectance analysis could be recorded on a JASCO model V-
6
70 spectrometer. Cyclic voltammetry (CV) experiments were
conducted on CHI660C Electrochemical Workstation by using a
three-electrode electrochemical cell (a glassy-carbon working
electrode, a saturated calomel electrode (SCE) as reference
electrode, and a platinum wire counter electrode).
and free radical polymerization, respectively.25c, 25d To efficiently Synthesis of BTP-CMP and TBTP-CMP
prepare advanced fine chemicals, however, further research on the
synthetic method and catalytic performance of TP-POP
photocatalysts is still necessary.
In this work, we targeted to develop TP-based CMPs (TP-CMPs) for
efficient metal-free photocatalysis in organic reactions. Through our
rational design, two representative thiophene derivatives, i.e. 2,2'-
bithiophene (BTP) and thieno[3,2-b]thiophene (TBTP), were selected
as FBBs to investigate the structure-activity relationships within
porous organic materials. Accordingly, we constructed two TP-CMPs
BTP-CMP and TBTP-CMP were prepared via Suzuki-Miyaura coupling
reaction. A two-necked flask was charged with TTDB (182.4 mg, 0.4
mmol), BTP-2Br (194.4 mg, 0.6 mmol) or TBTP-2Br (178.8 mg, 0.6
3 4
mmol), Pd(PPh ) (18.4 mg, 0.016 mmol). And then DMF (16 mL) and
2
M K CO aqueous solution (3.2 mL) were added into the flask. The
2
3
reaction mixtures were stirred and bubbled with a Ar ball for 30
minutes at room temperature. Then, the system was stirred under
1
50 oC and Ar atmosphere for 48 h. After cooling to ambient
temperature, the precipitate was filtrated and washed in turn with
deionized water, DMF, EtOH, dichloromethane and acetone. The
resulted solid was further purified by the Soxhlet extraction for 24h
with tetrahydrofuran (THF) and acetone as solvent, respectively.
(namely, BTP-CMP and TBTP-CMP) concisely via the Suzuki-Miyaura
coupling reaction (Scheme 1) in one step. Experiments proved that
the TP-CMPs could serve as stable, efficient and recyclable
heterogeneous photocatalysts in the synthesis of benzimidazoles.
Specifically, BTP-CMP exhibited more significant performance in
electron transfer and redox processes than TBTP-CMP. Furthermore,
o
After drying in vacuum for 12 h at 80 C, the reticular frameworks
were obtained as deep-yellow powder.
energy band structures and control experiment results revealed the Typical procedure for the preparation of 2-substituted
possible photocatalytic mechanism within the TP-CMP frameworks.
benzimidazole catalyzed by BTP-CMP under visible light
2
| J. Name., 2012, 00, 1-3
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Benzene-1,2-diamine or its derivatives (0.2 mmol), aromatic upling reaction in DMF, respectively. The obtainVeiedw AprtoicllyemOnelriniec
aldehyde (0.2 mmol), BTP-CMP (12 mg, 4.2 mol%), and MeOH (4.0 frameworks are insoluble in the selected soDlvOeIn:t1s0.s1u0c3h9/aDs0CdYim01e1t6h4yAl
mL) were added into a reaction tube. The reaction mixture was sulfoxide (DMSO), DMF, acetone, chloroform and THF.
stirred at room temperature under 10 W blue LEDs (the distance
The atomic-level linkages of the networks were verified by solid-
between LEDs and reaction tube is about 10 cm) and air. After the state 13C cross-polarization magic-angle spinning (CP/MAS) NMR
reaction was completed (monitored by TLC), the heterogeneous spectroscopy (Fig. 1). To identify the affiliation of carbon signals in
catalyst was isolated through centrifugation and thoroughly washed porous networks, we first studied the chemical shifts of carbon
by acetone (4 mL × 3). After removing the organic solvent under atoms in monomer BTP-2Br and TBTP-2Br through liquid 13C NMR
reduced pressure, the resulted crude products were further purified spectra (Fig. 1a and 1c) and 13C DEPT135 NMR technology. It is now
by flash column chromatography (with petroleum/acetone = 10/1 to clear that 122 (124) and 131 ppm were the signals of CH, while 138
5
/1 as eluent) to give 2-substituted benzimidazole.
ppm could be ascribed to the quaternary carbon atoms in BTP-2Br
or TBTP-2Br. Thus, for BTP-CMP, the peaks at 143, 123 and 136 ppm
correspond to the sp -carbon atoms on benzene rings and
bithiophene units (Fig. 1b). The chemical shifts are in accordance
with CP325c and MTP-1,25l which were prepared via direct C–H and
3
FeCl mediated oxidation coupling reaction by Liu et al and L.
2
Results and discussion
Designed synthesis and characterization of TP-CMPs
It has been demonstrated that TP and its derivatives are highly
electron-rich aromatic nucleus. A series of thiophene-containing
heterocycles, such as BTP and TBTP, are ubiquitous in electronics and
spintronics,29 organic light emitting diodes,30 dye-sensitized solar
cells,31 biosensing,32 organometallic chemistry,33 pharmaceutical
synthesis and protein receptor.34 Beneficial from the enhanced light
harvesting behaviour and electron-rich properties, thiophene-
embedded molecules or materials can also be used as efficient
photocatalysts.25c-g In order to realize the heterogenization of TP, we
selected trigeminal rigid monomer TTDB as the SBB, photoactive
BTP-2Br and TBTP-2Br as the FBBs (Scheme 1). Deep-yellow powder
BTP-CMP and TBTP-CMP were readily prepared via a concise one-
step route with 95% yield and 93% yield through Suzuki-Miyaura co-
Borchardt et al, respectively. Similar signals (125 and 145 ppm) of
Fig. 2 Nitrogen adsorption−desorption isotherms at 77 K and
corresponding pore size distribution profiles (insert) calculated from
desorption data using the NLDFT method for BTP-CMP (a) and TBTP-
CMP (b). STP = standard temperature and pressure.
Fig. 1 The liquid 13C NMR spectra (100 MHz, CDCl
) for the monomer
3
BTP-2Br (a), TBTP-2Br (c), and the solid-state 13C CP/MAS NMR
spectra (100 MHz) of BTP-CMP (b) and TBTP-CMP (d). The asterisks
denote the spinning sidebands.
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 3
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benzene rings can be found in the 13C NMR spectrum of TBTP-CMP
Fig. 1d), while the evident peaks at 118, 136 and 139 ppm are
View Article Online
DOI: 10.1039/D0CY01164A
(
ascribed to the carbon atoms from thieno[3,2-b] thiophene nodes.
Additionally, the Fourier transform infrared (FT-IR) spectra (Fig. S1†
and S2†) of TP-CMPs showed strong peak of thiophen ring at 792-
-
1 25e, 25l
8
00 cm .
These results indicate that thiophene blocks BTP and
TBTP were successfully embedded into the corresponding
conjugated skeleton.
Nitrogen sorption measurements at 77 K were used to investigate
the porosity of BTP-CMP and TBTP-CMP. As shown in Fig. 2, the two
frameworks exhibit type II sorption isotherms.26c Combine with the
pore size distributions profiles (insert images in Fig. 2), we observed
that both BTP-CMP and TBTP-CMP contain micropores, mesopores
and macropores. For BTP-CMP, the Brunauer− Emmett−Teller (BET)
Fig. 3 EDS mapping images of C and S for BTP-CMP (a-c) and TBTP-
CMP (d-f).
2
−1
surface area was 242 m g , while t-plot method revealed that the
contribution from mesopores and macropores surface area upto
structure optimization showed that the torsion angels of thiophene-
benzene in BTP-CMP were smaller than TBTP-CMP (Fig. S3†). The
resulted serious π-π stacking effects between the planers of
material was unfavourable to improve the surface areas of BTP-
CMP. While the slightly larger torsion angel enabled TBTP-CMP
o
o
8
3%. Replacement of DMF use THF (80 C), toluene (100 C), 1,4-
o
dioxane (120 C), N-methyl-pyrrolidone or N, N-dimethylacetamide
150 C), or to perform the reaction in DMF under 130 C didn’t
o
o
(
improve the BET surface areas of BTP-CMP (Table S1). The low
surface areas might due to the geometry of repeat units in BTP-CMP
network. A simple
2
−1
displayed higher BET surface areas (571 m g ) than BTP-CMP, and
the percentage of micropores surface area in TBTP-CMP was about
4
9
%
.
B
e
s
i
d
e
s
,
t
h
e
Fig 4. (a) UV/Vis absorption spectra and (b, c) Kubelka-Munk plots (to measure the band gap energy) for solid-state TP-CMPs. (d) Energy band
–•
positions of TP-CMPs and O
2
/O
2
measured by CV. (e) UV-vis absorption spectra and images of the tertiary amine radical cationic generated
atmosphere
by TP-CMPs under light and O
2
.
4
| J. Name., 2012, 00, 1-3
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DOI: 10.1039/D0CY01164A
ARTICLE
total pore volumes at 0.99 p/p
0
were 0.33 m g for TBT-CMP and Table 1 Optimization of the reaction conditionsa
3
−1
3
−1
0
.77 m g for TBTP-CMP.
H
N
NH2
NH2
visible light
catalyst, solvent
TGA under a nitrogen atmosphere showed that the as-synthesized
TP-CMPs possess exceptional thermostability (up to about 550 C,
Fig. S4†). The similar ultrastability can be found in porous aromatic
O
Cl
o
Cl
air, rt, 2 h
N
1a
2a
3a
frameworks (PAFs) and thiophene-embedded SNPs that constructed
with acetylene linkage.14a, 25h, 25l Both BTP-CMP and TBTP-CMP are
Entry catalyst (mol%)
solvent
MeOH
blue LEDs yield (%)b
1
2
3
4
5
6
7
8
9c
BTP-CMP (2.1)
5
65
amorphous as proved by powder X-ray diffraction (Fig. S5†). The SEM
images indicated that BTP-CMP and TBTP-CMP consisted of spherical
and irregular nanoparticles with porous surfaces, respectively (Fig.
TBTP-CMP (2.3)
BTP-CMP (2.1)
BTP-CMP (2.1)
BTP-CMP (2.1)
BTP-CMP (2.1)
BTP-CMP (2.1)
none
MeOH
MeOH
5
50
10
78
S6†). HR-TEM measurements demonstrated that the two networks
acetone 10
trace
trace
trace
trace
24
consisted of nanometer-scale pores (Fig. S7†). Energy-dispersive X-
ray spectroscopy (EDS) elemental mapping images in Fig. 3 suggested
that the elements C and S were homogeneously spread on the
THF
10
CH
CH
3
CN
Cl
10
networks of the TP-CMPs. The elemental composition (Fig. S8†)
detected by quantitative EDS agrees well with the theoretical values
and the element analysis results.
2
2
10
MeOH
MeOH
MeOH
MeOH
MeOH
MeOH
10
BTP-CMP (2.1)
BTP-CMP (2.1)
BTP-CMP (4.2)
BTP-CMP (6.2)
BTP-2Br (2.1)
10
18
Photocatalytic performance and recyclability of TP-CMPs
1
1
0
none
10
27
Optoelectronic properties were first studied to examine the
photocatalytic activity of TP-CMPs. As revealed by solid-state UV/vis
spectra, BTP-CMP and TBTP-CMP displayed broad absorption region
and similar edges at ca. 620 nm (Fig. 4a). The optical band gaps (Eg)
of BTP-CMP and TBTP-CMP, calculated via Kubelka-Munk function,
were 2.42 eV and 2.36 eV, respectively (Fig. 4b and 4c). Energy band
1
89 (98)d
92
12
10
1
3
10
29
a
b
General conditions: 1a (0.2 mmol), 2a (0.2 mmol), solvent (4.0 mL). Isolated
c
d
yields. no air. 2.5 h.
structures of TP-CMPs were assessed through cyclic voltammetry
c
(
CV) measurements (Fig. S9†). The conduction band positions (E ) vs.
SCE at -0.92 V (BTP-CMP) and -0.88 V (TBTP-CMP) were negative
activity of TP-CMPs in the conversion from ortho-diamine to 2-
arylbenzimidazoles (Table 1). After irradiation for 2 hours with 5 W
blue LEDs in methanol, the desired product 3a was obtained in 65%
and 50% yield for BTP-CMP and TBTP-CMP, respectively (Table 1,
entries 1 and 2). Contribute to the π-π stacking effects, energy band
structures and porosity in TP-CMPs, the more remarkable catalytic
effects displayed in BTP-CMP than TBTP-CMP was reasonable.
•−
22e
g
c
enough to reduce O
the valence band positions (E ) vs. SCE of BTP-CMP and TBTP-CMP
2
to O
2
(-0.86 V vs. SCE). Combined E with E ,
v
were estimated as 1.50 V and 1.48 V, respectively (Fig. 4d).
*
Upon exposing to light, the excited materials BTP-CMP and TBTP-
*
CMP would effectively promote the generation of blue-coloured
1
O
,4-bis(dimethylamino)benzene-cationic radical (0.12 V vs. SCE) and
•–
2
, which were mediated via the electron transfer from tertiary
v
Obviously, the faster transfer of electrons, higher E and more
2
2e, 22g
amine to O
2
(Fig. 4e)
.
The higher absorbance of the obtained
c
negative E (Fig. 4d) guarantee the light-induced redox process
deeper blue cationic radical solvents (Fig 6e and insert) implied that
BTP-CMP possess superior photocatalytic activity than TBTP-CMP.
This is due to the existing superior π-π stacking effects in BTP-CMP
facilitate the electronic transmission along the π-skeletons.35
Besides, the catalytic results are consistent with the energy band
positions in Fig. 4d, and suggest that TP-embedded CMPs can used
as metal-free catalysts in photoredox organic reactions.
As one of the most common heterocyclic structure,
benzimidazoles endow drugs with amazing bioactivity for insects,
sphaerotheca fuliginea, penicilliosis, cancer cells, heart disease and
HIV etc. 36 Additionally, the significant moieties can be widely found
in polybenzimidazole fibres, porous organic networks and
photoelectric materials.37 Thus, we initially examined the catalytic
easier in BTP-CMP. Meanwhile, the more affluent macro/meso
pores provide convenience for the mass transfer of substrates and
products. An enhanced catalytic efficiency could be obtained with
7
(
7
8% yield when the light source was replaced by 10 W blue LEDs
Table 1, entry 3). As confirmed by experiments (Table 1, entries 3-
), aprotic solvents such as acetone, acetonitrile, THF and
dichloromethane could not give encouraging results. Investigation
on the influence of catalyst loading revealed that an appropriate
increase of BTP-CMP could improve the yield (Table 1, entry 11).
Nevertheless, further increase of the BTP-CMP (6.2 mol%) loading
didn’t give marked improvement to the yield (Table 1, entry 12),
which was ascribed to the higher concentration solid catalyst might
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Table 2 Preparation of 2-arylbenzimidazoles with aldehydes and filtration, evaporation and washing, see the ESI†). This result
View Article Online
aromatic diamines catalyzed by BTP-CMP under visible light a
DOI: 10.1039/D0CY01164A
indicated that TP-CMPs might have potential applications in
industrial catalysis.
H
N
NH2
NH2
BTP-CMP
Ar CHO
2
The catalytic stability and recyclability of TP-CMPs were examined
with recovered BTP-CMP to perform the catalytic reaction as
displayed in Table 1 under the standard conditions. We found BTP-
CMP could be reused for at least 15 times with remarkable catalytic
R
R
Ar
MeOH, 10 W blue LEDs
N
air, rt
1
3
N
N
N
Cl
N
H
N
H
N
activity (96-98% yield, Fig. S12†). Nevertheless, the decrease of BET
H
Cl
3
a, 2.5 h, 98% yield
5 h, 1.06g, 93% yield)
2
-1
2
-1
3
(
b, 3 h, 93% yield
3c, 4 h, 91% yield
surface area (242 m g to 30 m g ) caused the reaction time to be
prolonged (Fig. S12† and S13†). These results indicate that the
porosity have further effects on the catalytic abilities of POPs.
Meanwhile, the recorded FT-IR spectra (Fig. S14†) demonstrated that
the BTP-CMP almost maintained its skeleton structure after 15
iterative runs. These results confirmed the notable reusability and
high stability of the designed TP-CMPs as photocatalyst.
b
(
3.5 h, 92% yield)c
N
N
N
CH3
CN
F
N
H
N
H
N
H
3
(
d, 3 h, 96% yield
3 h, 95% yield)
3e, 5 h, 92% yield
3f, 3.5 h, 94% yield
c
N
Br
N
N
N
H
N
H
Catalytic mechanism
N
H
3
i, 2.5 h, 98% yield
3
g, 3 h, 94% yield
3h, 4 h, 92% yield
In order to insight into the reaction process, we tested the yield of
the possible intermedium I and II (Scheme 2A). In fact, the yield of I
was up to 92% after 0.25 h, and remained about 90% to >99% yield
within 12 h, while II and 3a were not be observed in liquid NMR
Br
N
Cl
Cl
N
N
Cl
N
H
N
H
N
H
3
(
k, 3 h, 96% yield
3j, 2.5 h, 97% yield
3l, 3 h, 96% yield
spectra (Fig. S15†). Furthermore, intermedium I could translate into
the product 3a quickly with 85% yield under visible light and BTP-
CMP, however, the reaction proceeded slowly in the absence of BTP-
CMP within the same time (Scheme 2B, i and ii). The results above
implied that: 1) compound I may be the key intermedium that take
part in the subsequent photocatalytic process; 2) both catalyst BTP-
CMP and visible-light were essential to the reaction here.
4 h, 94% yield)c
a
Reaction conditions: aromatic diamine (0.2 mmol), aldehyde (0.2 mmol),
BTP-CMP (12 mg, 4.2 mol%), MeOH (4.0 mL). Isolated yields. b Scale-up
experiment: 1a (5 mmol), 2a (5 mmol), BTP-CMP (180 mg, 2.5 mol%), MeOH
100 mL). c TBTP-CMP (10.8 mg, 4.2 mol%) as catalyst.
(
Based on the results of control experiments above and those
homogeneous photocatalysis systems36b, 38 for the synthesis of
benzimidazoles, we proposed a possible reaction mechanism as
block the transmission of visible light and resulted in ineffective light
absorption. Further experiment demonstrated 4.2 mol% BTP-CMP
was adequate for the 0.2 mmol scale substrates and produced 3a in
9
8% yield within 2.5 h. Meanwhile, control experiments indicated
that air (O ), light and photocatalysts were necessary to get the same
2
(
A)
Cl
result shown as entry 3 in Table 1. It should be noted that BTP-2Br as
catalyst didn’t give a favourable yield (29%, entry 13), implying short-
range π-π conjugated system was disadvantageous for
photocatalytic activities. Therefore, the reaction conditions for the
catalytic synthesis of 2-arylbenzimidazoles (3) were then set as 12 mg
NH2
NH2
Yield (%)
Entry t (h)
N
I
II
I
1
2
3
4
0.25
0.5
1.0
12
92
90
>99
95
-
1a
NH2
MeOH, rt
in dark
-
H
N
OHC
Cl
-
Cl
2a
N
H
-
2
of BTP-CMP, methol as the solvent, with air (O ) and 10 W blue LEDs
at room temperature.
II
(B)
Cl
5
W blue LEDs,
MeOH, rt, air, 2h
H
N
N
With the optimal reaction condition in hand, we next explored the
substrate scope for the reaction system. As shown in Table 2, the as-
prepared BTP-CMP works very well for symmetrical/unsymmetrical
Cl
i) BTP-CMP(12 mg),85% yield
ii) no cat., 37% yield
N
NH2
3a
I
aromatic diamines and various aldehydes. All substrates with Scheme 2 Control experiments.
different substituent groups, including 1-naphthaldehyde (3g), 2-
NH2
NH2
NH2
naphthaldehyde (3h), 4,5-dimethylbenzene-1,2-diamine (3k), and
,5-dichlorobenzene-1,2-diamine (3l), could furnish the
2
-H O
TP-CMP+
O2
O2 e-
Ar-CHO
N
Ar
Ar
4
I
e-
corresponding benzimidazole derivatives smoothly in 2.5-5.0 h with
excellent yields (Table 2, 91–98%) and without by-products.
Meanwhile, TBTP-CMP also displayed comparable catalytic effects as
its counterpart BTP-CMP with 92-95% yield for 3b, 3d and 3k.
Furthermore, gram-scale photocatalytic synthesis of 3a was
successful with 93% yield (1.06 g) through concise procedures (i.e.
TP-CMP
*
NH2
O2 HO2
H2O2
N
(i)
N
Ar
Ar
N
(ii) intramolecular
N
H
H
N
H
TP-CMP
III
HO2
cyclization
E(III/I) = 0.45 V. vs. SCE
IV
3
Scheme 3 Proposed mechanism for the transformation of benzene-
1
,2-diamine to benzimidazole in the presence of TP-CMP under light.
This journal is © The Royal Society of Chemistry 20xx
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CP al et aa lsy es i ds oS c ni eo nt c ae d &j uTs et c mh na or gl oi ng sy
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described in Scheme 3. Initially, the excited materials (TP-CMP*) Research Projects in Henan Colleges and UnivVeierwsiAtriteicsle O(nNlinoe.
would generate upon ground-state TP-CMP was irradiated with 18A150006). We thank Xiaoyu Liang and WDOeIn: b10o.10S3h9e/nD0aCtY0H1e1n6a4An
appropriate light. Oxygen molecule in air captured an electron from Agricultural University for their valuable comments.
TP-CMP*, and then produced O –•
and TP-CMP . Meanwhile, the
+
2
imine I that derived from aromatic diamine and aldehyde would
+
Notes and references
provide an electron (EI/II = 0.45 V, Fig. S16†) for TP-CMP to recover
TP-CMP. The resulted cation radical intermediate III could release a
1
2
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–•, and generated the radical
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6
In summary, by incorporating well-selected S-heterocycle monomers
into polymeric framework through a “bottom-up” strategy, we have
successfully developed thiophene-functionalized porous networks,
TP-CMPs, via one step Suzuki-Miyaura coupling reaction. Owing to
the property of electron-rich of thiophene derivatives, π-π
conjugated TP-CMPs displayed appropriate energy band structures
and good photochemical activities. We found the as-synthesized
frameworks showed good photocatalytic activities to the reaction
between aldehyde and diamine. Specially, bithiophene-embedded
BTP-CMP displayed preferable catalytic effects (91-98% yield),
excellent reusability (at least 15 times, 96-98% yield) and high
stability in the synthesis of 2-arylbenzimidazoles under visible light.
Meanwhile, we outline the possible reaction mechanism within
heterogeneous system. Considering the tunability of functional
monomers and structural features of POP materials, we expect that
CMPs represented by TP-CMPs would become a class of efficient
photocatalysts and toward the industrial catalysis for fine chemicals.
(
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Author contributions
Wan-Kai An and Zhenliang Pan conceived the project. Wan-Kai An,
Shi-Jia Zheng, and Ya-Nan Du prepared the CMPs and performed the
experiments on characterization and photocatalysis. Xiaobiao Liu
and San-Yuan Ding conducted the calculations. Wan-Kai An and
Yuchen Qin carried out the energy band structures analyses. Wan-
Kai An, Song Jiang, Pi-Feng Wei, Zhan-Qi Cao and Meirong Song
analyzed the catalytic mechanism. Shi-Jia Zheng and Wan-Kai An
wrote the original manuscript. San-Yuan Ding, Zhenliang Pan, and
Zhi-Jun Li revised the manuscript. All authors discussed the
comments and contributed to generation of the manuscript.
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Acknowledgements
The authors gratefully acknowledge the National Natural Science
Foundation of China (No. 21702047 and 21702049), the Key Scientific
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 7
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DOI: 10.1039/D0CY01164A
The graphical and textual abstract for the Table of contents entry:
Thiophene-embedded Conjugated Microporous Polymers for Photocatalysis
a
a
a
b
c
a
a
Wan-Kai An,* Shi-Jia Zheng, Ya-Nan Du, San-Yuan Ding,* Zhi-Jun Li, Song Jiang, Yuchen Qin,
a
d
a
a
a
Xiaobiao Liu, Pi-Feng Wei, Zhan-Qi Cao, Meirong Song, and Zhenliang Pan*
“Bottom-up” embedding of thiophene derivatives into CMPs for highly efficient heterogeneous
photocatalysis.