A Cross-linked Conjugated Polymer Photosensitizer Enables Efficient Sunlight-Induced Photooxidation

Article abstract of DOI:10.1002/anie.201811067

Photooxidation under sunlight has potential in organic synthesis, bacterial killing, and organic waste treatment. Photosensitizers (PSs) can play an important role in this process. High ¹O₂ generation efficiency and excellent photostability under sunlight, as well as easy recyclability are ideal properties for PSs, but are not easy to achieve simultaneously. Herein, a pure organic porous conjugated polymer PS, CPTF, shows great photostability, large specific surface area, and high ¹O₂ generation efficiency under sunlight for photooxidation. For the oxidation of aromatic aldehyde to aromatic acid, the PS catalyst shows excellent recyclability, and enables solvent-free reactions in high yields both under direct sunlight and simulated AM 1.5G irradiation. In addition, the successful application of CPTF as an antibacterial agent and organic waste decomposition under simulated AM 1.5G irradiation indicates the potential of CPTF in sunlight-induced waste water treatment.

Full text of DOI:10.1002/anie.201811067

A Journal of the Gesellschaft Deutscher Chemiker
Angewandte
Chemie
International Edition
www.angewandte.org
Accepted Article
Title: A Cross-linked Conjugated Polymer Photosensitizer Enables
Efficient Sunlight-induced Photooxidation
Authors: Wenbo Wu, Shidang Xu, Guobin Qi, Han Zhu, Fang Hu,
Zitong Liu, Deqing Zhang, and Bin Liu
This manuscript has been accepted after peer review and appears as an
Accepted Article online prior to editing, proofing, and formal publication
of the final Version of Record (VoR). This work is currently citable by
using the Digital Object Identifier (DOI) given below. The VoR will be
published online in Early View as soon as possible and may be different
to this Accepted Article as a result of editing. Readers should obtain
the VoR from the journal website shown below when it is published
to ensure accuracy of information. The authors are responsible for the
content of this Accepted Article.
To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.201811067
Angew. Chem. 10.1002/ange.201811067
Link to VoR: http://dx.doi.org/10.1002/anie.201811067
http://dx.doi.org/10.1002/ange.201811067

10.1002/anie.201811067
Angewandte Chemie International Edition
COMMUNICATION
A Cross-linked Conjugated Polymer Photosensitizer Enables
Efficient Sunlight-induced Photooxidation
Wenbo Wu,+ Shidang Xu,+ Guobin Qi, Han Zhu, Fang Hu, Zitong Liu, Deqing Zhang, and Bin Liu*
Abstract: Photooxidation under sunlight has great potentials in
organic synthesis, bacterial killing, organic waste treatment, etc.
Photosensitizers (PSs) often play a very important role in this process.
High 1O2 generation efficiency and excellent photostability under
sunlight, as well as easy recyclability are ideal properties for PSs used
for photooxidation, which are not easy to achieve simultaneously.
Herein, a pure organic porous conjugated polymer PS of CPTF was
designed and synthesized to show great photostability, large specific
surface area and high 1O2 generation efficiency under sunlight for
photooxidation in different applications. Taking the oxidation of
aromatic aldehyde to aromatic acid as an example, the PS catalyst
shows excellent recyclability, which enables solvent-free reactions in
high yields both under direct sunlight and simulated AM1.5G
irradiation. In addition, the successful application of CPTF in bacterial
killing and organic waste decomposition under simulated AM1.5G
irradiation indicates the potential of CPTF in sunlight-induced waste
water treatment.
can further oxidize the organic compounds to yield desirable
targets.[3-5]
During the past several years, alcohol oxidation,[3] aldehyde
oxidation,[3c,4] bromination reaction,[5] and oxidative Ugi-type
reaction,[6] etc. have been realized using PS-assisted
photooxidation. However, most of these reactions require a high
power light source (usually 300-1000 mW/cm2),[5-8] much higher
than that of sunlight (100 mW/cm2 for AM1.5G) to proceed, due to
the lack of highly efficient PSs designed for specific reactions. As
PSs may react with the ROS they produce, the use of high power
irradiation makes them more vulnerable to photobleaching with
reduced photostability, which prevents them from being used
under long-term light irradiation.[9] Besides, the relatively narrow
absorption of the existing PSs is another issue, which requires
most reactions to be driven by blue LED[5,7] or other high power
lamps[6,8] rather than sunlight. In fact, when the same organic
reactions were driven by sunlight or natural light, the oxidation
efficiency became very low.[8] Due to the lack of suitable PSs, it
remains challenging for these light-induced oxidation reactions to
meet the requirements of green chemistry.
Green chemistry, which focuses on the design of products and
processes with minimized usage and generation of hazardous
substances, has attracted much research interest from the
synthetic chemistry community.[1] Reactions that could proceed at
room temperature or relatively low temperature, using water as
the solvent or solvent-free in the presence of non-toxic or low-
toxic recyclable catalysts with easy purification are regarded as
green reactions.[1] Despite of much effort, all the key features of
green reactions are often not very easy to meet simultaneously.
Light-driven chemical reactions, especially sunlight-driven
chemical reactions, have attracted much attention as potential
green reactions due to their relatively energy conserving and
environmentally benign synthetic processes.[2] Among these
reactions, light-driven oxidation of organic compounds in the
presence of photosensitizers (PSs) and oxygen is of particular
interest.[3-5] Upon light irradiation, the excited PSs help convert
molecular oxygen to singlet oxygen (1O2) or other reactive oxygen
species (ROS) with strong oxidizing property (Figure S1), which
For metal-based inorganic and complex PSs, their potential
toxicity and high cost together with the limited availability of
precious metals in nature make them not ideal for green
oxidation.[5] Therefore, the recent years have witnessed the rapid
development of pure organic PSs. Different strategies, such as
introducing heavy atoms, modulating intersystem crossing,
improving light absorption, reducing non-radiative decay, etc,
have been successfully used to effectively improve the ROS
generation of organic PSs.[10] As most of these PS designs were
driven by their applications in photodynamic therapy (PDT),
photostability is less of the concern since the duration of PDT
usually lasts only for several minutes. In fact, many of the most
successful commercial PSs, such as Rose Begal (RB), show
poor photostability, which makes them less suitable for
photooxidation reactions. In one of the recent publications, RB
was integrated with porous conjugated polymers for improving its
photostability.[8] However, due to the narrow absorption of RB, the
corresponding reaction still requires light source rather than
sunlight to activate.[8] As such, how to develop highly stable and
efficient PSs is the key to drive the success of sunlight-induced
photooxidation reactions.
[*]
Dr. W. Wu,+ Mr. S. Xu,+ Mr. G. Qi, Dr. F. Hu, Prof. B. Liu
Department of Chemical and Biomolecular Engineering
National University of Singapore
4 Engineering Drive 4, Singapore, 117585
E-mail: cheliub@nus.edu.sg
Prof. H. Zhu
Key Laboratory of Synthetic and Biological Colloids
Ministry of Education
School of Chemical and Material Engineering
Jiangnan University
Wuxi, 214122, China
Prof. Z. Liu, Prof. D. Zhang
Beijing National Laboratory for Molecular Sciences
Organic Solids Laboratory
Institute of Chemistry CAS
Beijing, 100190, China
+ These authors contributed equally to this work.
Figure 1. Design principle of cross-linked conjugated polymer PS.
Recently, we observed that the photostability of many small
molecular dyes could be improved upon polymerization.[4a,5,8,11]
More importantly, the photosensitization capability of small
Supporting information for this article is given via a link at the end of
the document.
This article is protected by copyright. All rights reserved.

10.1002/anie.201811067
Angewandte Chemie International Edition
COMMUNICATION
molecular PSs may also be improved upon polymerization.[11]
Motivated by these observations, we started to design
CPTF under the same condition, respectively, which are similar to
that of RB (19.8 nmol of ABDA consumed by 0.01 mg RB under
the same condition), confirming the highly efficient 1O2 generation
by both polymers. In addition, after AM 1.5G irradiation for 4 h,
the 1O2 generation efficiencies of CPTF, PTF, DTF and RB
(Figure 2C) are nearly 100%, 83%, 67% and <1% of their original
values, respectively, indicating excellent photostability of CPTF in
terms of 1O2 generation. As shown in Figure 2D, in powders, DTF
shows very bright emission centred at 632 nm. For PTF, its
emission peak is red-shifted to 668 nm due to extended
conjugation as compared to that for DTF, but the emission
intensity is dropped to one quarter of that for DTF. However, there
is nearly no emission observed for CPTF. From DTF to PTF, then
to CPTF, the improved 1O2 generation efficiency upon light
illumination agrees with the gradually decreased fluorescence
trend (Figure 2D), as a result of the competition between
photosensitization and light emission (Figure S1). As shown in
Figure S7, the Brunauer−Emmet−Teller (BET) surface area of
CPTF is calculated to be 117.2 m3/g, much larger than that of PTF
(14.2 m3/g), which represents another advantage of CPTF to be
used for photooxidation. The morphology of CPTF was
investigated by Scanning Electron Microscope (SEM), and the
result is presented in Figure S8. It shows a fused particle-like
structure, which should be driven by the strong π-π stacking
between extended π-system during the cross-linking process.[5]
1
photostable PSs with high O2 generation efficiency via a three-
step process. In the first step, we selected DTF (Figure 1A) as a
model compound, as it shows a broad absorption peak and good
photostability.[12] In DTF, triphenylamine (TPA) is used as the
donor and fumaronitrile (FN) is used as the acceptor. The phenyl
rings between donor and acceptor can separate the HOMO-
LUMO distribution of DTF, which is helpful to promote the
1
intersystem crossing (ISC) process and favor O2 generation.[13]
Subsequently, a conjugated polymer PTF (Figure 1A) with the
1
same donor and acceptor as DTF was designed to improve O2
generation. Meanwhile, due to its elongated conjugation, a
broader absorption peak is expected for PTF to better match the
sunlight spectrum than DTF does. In the last step, to optimize the
PS functions, such as to endow the PS with easy separation and
recyclability after the photooxidation reaction, to increase its
specific surface area for catalytic reactions and to further enhance
its photostability in photooxidation,[5] a cross-linked porous
conjugated polymer CPTF (Figure 1A) was further designed
based on PTF. Detailed analysis and characterization revealed
that CPTF showed good performance in sunlight-induced green
photooxidation. Under natural sunlight or simulated AM1.5G
irradiation, benzaldehyde can be converted to benzoic acid
without any solvent using CPTF as the photooxidation catalyst.
Inspired by this result, we further investigated the performance of
CPTF in bacterial killing and organic waste decomposition under
simulated AM1.5G irradiation, and the result showes that CPTF
has great potential in sunlight-induced wastewater treatment.
According to the literature,[12] DTF was prepared by Suzuki
reaction between TPA-2B and FN-2Br in a yield of 82.4%.
Through Suzuki coupling polymerization between triphenylamine-
based monomer TPA-2B (or TPA-3B) and fumaronitrile-based
monomer FN-2Br, both PTF and CPTF were synthesized easily
(Scheme S1) with 58.8% and 85.4% yields, respectively, whose
structures have been confirmed by NMR spectra (Figure S2-S5).
In the solid 13C NMR spectrum of CPTF, the broad peak from 140
to 150 ppm can be assigned to the carbon next to the nitrogen
atom in TPA moieties (marked with a in Figure S5), while the peak
from 116 to 120 ppm can be assigned to the nitrile group (marked
with b in Figure S5) from the FN moieties, indicating successful
polymerization.
The linear polymer PTF can be easily dissolved in common
organic solvents, such as dichloromethane and tetrahydrofuran
(THF), while the cross-linked CPTF is insoluble in any common
solvent. Both PTF and CPTF show very board UV-vis diffuse
reflectance spectra from 300 to 700 nm (Figure 2A) in powders.
In comparison with the UV-vis spectra of DTF and RB, which
show much narrow absorption peak centred at 480 and 550 nm,
respectively (Figure 2A), the broad peak of CPTF is very
beneficial to matching the sunlight radiation spectrum (Figure S6).
Figure 2. (A) Normalized UV-vis diffuse reflectance spectra of PTF and CPTF
in powders, and UV-vis absorption spectra of DTF and RB in THF/water = 1/99
(v/v). (B) Degradation rates of ABDA by DTF, PTF and CPTF in water; A0 and
A are the absorbance of ABDA in the presence of photosensitizers at 378 nm
before and after AM1.5G irradiation, respectively. (C) The photostability was
tested by comparing the relative 1O2 generation efficiencies of DTF, PTF and
CPTF (dispersed in water) under AM 1.5G irradiation for different time.
Conditions: [ABDA] = 5×10-5 M, [PS] = 0.01 mg/mL. (D) PL spectra (λex = 480
nm) of DTF, PTF and CPTF in solid state. (E) The Kohn-Sham frontier orbital
analysis of different model compounds (S is short for singlet, T is short for triplet)
by TD-DFT (Gaussian 09/B3LYP/6-31G(d)).
1
Subsequently, the O2 generation efficiencies of DTF, PTF and
CPTF in aqueous media were measured by using 9,10-
anthracenediyl-bis(methylene)dimalonic acid (ABDA) as the
indicator (Figure 2B). From the reduced ABDA absorbance in the
presence of DTF (0.01 mg/mL), it is calculated that 5.2 nmol of
ABDA can be consumed by 0.01 mg of DTF under simulated AM
1.5G irradiation for 1 min. After polymerization, 18.9 nmol, and
20.8 nmol of ABDA can be consumed by 0.01 mg of PTF and
This article is protected by copyright. All rights reserved.

10.1002/anie.201811067
Angewandte Chemie International Edition
COMMUNICATION
Time-dependent
density
functional
theory
(TD-DFT)
Singapore) with a conversion yield of 81.2 %, which is similar to
that under simulated AM 1.5G illumination.
investigation[14] was then performed to understand the different
1O2 generation efficiencies of DTF, PTF and CPTF. Three model
compounds, which refer to the simplified DTF, PTF and CPTF,
were used for calculation (Figure S9). Their HOMO-LUMO
distributions at optimized structures are presented in Figures S10-
S12. For the three model compounds, the HOMO is mainly
distributed at the TPA moieties, while the LUMO is mainly
distributed at the FN moieties, indicating good HOMO-LUMO
separation, which favours for 1O2 generation.[13] The energy levels
of their singlet and triplet excited states were subsequently
studied by TD-DFT method (Figure S13). It is easily seen that the
differences between different energy levels of PTF and CPTN are
much smaller than that of DTF. Detailed modelling results indicate
that, in DTF, only S1 to T1 and T3 transitions are possible (Figures
2E, S14, and Table S1). In PTF and CPTF, there are 8 possible
ISC channels (S1 to T1, T2, T3, T4, T6, T9, T10, and T11, Figures 2E,
S15, and Table S2), and 10 possible ISC channels (S1 to T1, T2,
T3, T4, T5, T6, T7, T8, T10, and T11, Figures 2E, S16, and Table S3),
respectively. The increased numbers of energy transition
channels are beneficial to ISC process to favour 1O2 generation.
To understand the oxidation mechanism, four control experiments
were performed by adding differernt ROS scavengers to the
reaction. As shown in Figure S17, by adding benzoquinone
(superoxide scavenger), catalase (H2O2 scavenger), and TEMPO
(hydroxyl radicals scavenger), respectively, the conversions were
nearly the same as before. On the contrary, when adding NaN3,
an 1O2 scavenger, the conversion efficiency was decreased
sharply from 87.1% to 36.2%, indicating that 1O2 is the key ROS
during the oxidation process. Therefore, the mechanism of the
photooxidaion reaction can be described as the following: under
1
light irradiation of CPTF, molecular O2 is first transferred to O2,
which further oxides benzaldehyde to benzoic acid.
Additionally, some other substrates, with different electron-
withdrawing or electron-donating groups, and varying amount of
aldehyde groups, were also tested to demonstrate the general
applicability of CPTF for photooxidation (Figure 3B). The electron-
withdrawing group linked to the aldehyde can enhance its
electropositivity, making the aldehyde group more easily to be
oxidized. Therefore, aldehyde with electron-withdrawing groups,
such as -F and -NO2, showed a higher conversion yield than those
with
electron
donating
groups.
As
for
4-
(diethylamino)benzaldehyde, due to the very strong electron-
donating ability of diethylamino group, the reaction did not occur
under our reaction condition. To demonstrate the value of the
photooxidation
reaction,
we
further
selected
5-
hydroxymethylfurfural as the reactant, as its oxidation products,
such as 2,5-furandicarboxylic acid, are important substitutes for
petro chemicals.[15] As shown in Figure 3B, under simulated
AM1.5G irradiation (100 mW/cm2) for 16 h, a conversion of 78.2%
can be achieved by using CPTF as the photocatalyst. As
compared to the literature,[3c] which required 0.5 W/cm2 light
illumination for 14 h to yield the same product, our approach
shows clear advantages.
For liquid aldehydes, we have also developed a solvent-free
method to photooxidize them with high conversion yields. As the
Figure 3. (A) The conversion of benzaldehyde photooxidation by using different
PSs as the catalyst under AM1.5G irradiation. Benzaldehyde: 1 mmol, PS: 1 mg,
CH3CN: 1 mL. (B) The reaction results of different reactants by using CPTF as
photosensitizer. Reactant: 1 mmol, PS: 1 mg, CH3CN: 1 mL. Conversion in
parentheses refers to solvent-free reaction under the following condition:
Reactant: 10 mmol, PS: 2 mg. (C) The recycling process of sunlight-induced
photooxidation of benzaldehyde.
1
lifetime and effective diffusion distance of O2 are very short,[16]
the absence of solvent reduces the distance between the
generated 1O2 and aldehyde molecules, which is beneficial to
oxidation. Even when the amount of CPTF used was decreased
to 20% of that used in the same reaction with solvent, all three
examples showed high conversion efficiencies (Figure 3B).
Based on this result, we further scaled up this photoreaction to a
slightly larger scale. Under simulated AM1.5G irradiation for 6 h,
10 g of liquid benzaldehyde can be easily converted to solid
benzoic acid with a conversion yield of 74.2% in the presence of
CPTF (Figure S18).
Subsequently, the photooxidation catalysed by CPTF was studied
using benzaldehyde as a model compound. As shown in Figure
3A, by using CPTF as the PS photocatalyst, 87.1% of
benzaldehyde could be oxidized to benzoic acid under simulated
AM 1.5G irradiation for 4h. Under the same conditions, a similar
conversion of 82.4% can be acheived by using PTF as the
Considering the excellent photostability of CPTF and its poor
solubility in any organic solvent, we further designed a recycling
process for the photooxidation of benzaldehyde (Figure 3C). One
starts with benzaldehyde and CPTF in a flask, under simulated
AM1.5G irradiation for 6h, ethanol was added to the reaction
system to dissolve the benzoic acid and the unreacted
benzaldehyde, but not CPTF. Therefore, the photocatalyst can be
recovered by simple filtration. After ethanol removal, the pure
1
catalyst, since the O2 generation efficiency between CPTF and
PTF is smilar. As reference, by using DTF and RB as the PSs,
the conversion efficiencies were only 34.2%, and 42.3%,
respectively. Although the 1O2 generation efficiency of RB is
similar to that of CPTF, the significantly lower conversion
efficiency by RB is due to its poor photostability. By using sunlight
as the light source, benzaldehyde could also be oxidized to
benzoic acid within 4 h (from 10 am to 2 pm on a sunny day in
This article is protected by copyright. All rights reserved.

10.1002/anie.201811067
Angewandte Chemie International Edition
COMMUNICATION
benzoic acid can be obtained by recrystallization from hexane.
The filtrate contains the unreacted benzaldehyde and a little
mount of benzoic acid, which can be reused for the next cycle of
reaction. Through each cycle, 6~6.5 g of benzoic acid can be
obtained, if we keep 10 g of benzaldehyde at the feed. Meanwhile,
the catalytic activity of CPTF was also tested (Figure S19). After
10 cycles, the activity of CPTF was about 85% as that for the first
run. As such, the reaction can be driven by sunlight without any
solvent in a large scale, and the product can be easily purified. In
addition, the catalyst of CPTF and unreacted reactant can be
easily recycled, which meet all the requirements of green
reactions.
under AM1.5G irradiation. As shown in Figure S20, once the
bacteria were treated with CPTF under AM1.5G irradiation for 1
h, serious collapse and merge in membranes were observed.
After the same irradiation for 2 h, some holes were observed in
the bacteria. In contrast, the morphologies of bacteria exhibited
clear edges and smooth bodies for the control group (bacteria
without CPTF treatment). The positive results on organic waste
decomposition and bacterial killing indicated good performance of
CPTF in sunlight-induced wastewater treatment.
In conclusion, a cross-linked porous conjugated polymer PS of
CPTF was designed and synthesized via A3+B2 Suzuki
polymerization. CPTF shows good 1O2 generation efficiency
under sunlight irradiation, excellent photostability, and large
specific surface area for photooxidation. Meanwhile, its excellent
photostability and poor solubility endow it with good recyclability.
Under simulated AM1.5G irradiation, the light-induced organic
synthesis by using oxidation of aldehyde to acid as the example,
and light-induced wastewater treatment by using organic waste
decomposition and bacterial killing as the example indicate that
CPTF is an excellent photocatalyst for sunlight-induced
photooxidation. These results will open up new opportunities for
green chemistry.
Figure 4. (A) The degradation rates of Rhodamine 6G (1×10-4 M) by CPTF and
Rose Begal (0.1 mg/mL); A0 and A are the absorbance of Rhodamine 6G in
the presence of the CPTF and Rose Begal at 530 nm before and after AM1.5G
irradiation, respectively. (B) Photos of Rhodamine 6G solutions with CPTF
before and after AM1.5G irradiation for 2h. From left to right: before irradiation;
after irradiation; after irradiation and then filtration. (C) The killing efficiency of
CPTF (0.1 mg/mL) to S. aureus (1×107 counts/mL) under AM1.5G irradiation for
different times. (D) Plate photographs for S. aureus on LB agar plate
supplemented with CPTF with AM1.5G irradiation for different times and then
grew overnight. From left to right: 0 h, 1 h, and 2 h.
Acknowledgements
We thank the Singapore NRF Competitive Research Program
(R279-000-483-281), NRF Investigatorship (R279-000-444-281),
and National University of Singapore (R279-000-482-133) for
financial support.
Keywords: photosensitizers • singlet oxygen • photooxidation •
sunlight-induced organic synthesis • sunlight-induced
wastewater treatment
Besides organic synthesis, another photooxidation application is
photo-induced wastewater treatment. Under light irradiation, the
generated 1O2 by PSs can ablate commonly seen
microorganisms (such as bacteria, molds and fungi) and
decompose organic waste in water to realize wastewater
treatment.[9] Herein, Rhodamine 6G, and staphylococcus aureus
(S. aureus, ATCC 6538, one of Gram-positive bacteria) were used
as the examples of organic waste, and microorganism,
respectively, to demonstrate the sunlight-induced wastewater
treatment ability and the results are presented in Figure 4. In the
presence of CPTF (0.1 mg/mL), nearly all the Rhodamine 6G
(1×10-4 M) can be decomposed under simulated AM1.5G
irradiation for 2h (Figure 4A). As a reference, only 25% of
Rhodamine 6G was decomposed by RB under the same
condition. In addition, CPTF can be recovered by filtration easily
(Figure 4B). The bacterial killing efficiency of CPTF was then
performed to determine the percentage of live cells by a traditional
colony counting method. After AM1.5G irradiation for 1h, the
percentage of living cells decreased sharply and the relative
viability of S. aureus was lower than 5% (Figures 4C and 4D, initial
concentration: 1×107 counts/mL), and after 2 h irradiation, nearly
all the S. aureus can be killed by the generated 1O2 from CPTF.
To obtain further evidence for the antimicrobial activity of CPTF,
field emission SEM was employed to monitor the morphological
changes of the bacteria before and after treatment with CPTF
[1]
[2]
I. T. Horváth, P. T. Anastas, Chem. Rev. 2007, 107, 2167-2168.
a) D. Ravelli, M. Fagnoni, T. Fukuyama, T. Nishikawa, I. Ryu, ACS Catal.
2018, 8, 701-713; b) F. E. Osterloh, ACS Energy Lett. 2017, 2, 445-453;
c) D. Ravelli, D. Dondi, M. Fagnoni, Angelo Albini, Chem. Soc. Rev.
2009, 38, 1999-2011.
[3]
a) Y.-Z. Chen, Z. U. Wang, H. Wang, J. Lu, S.-H. Yu, H.-L. Jiang, J. Am.
Chem. Soc. 2017, 139, 2035-2044; b) Y. Chen, J. Zhang, M. Zhang, X.
Wang, Chem. Sci. 2013, 4, 3244-3248; c) S. Xu, P. Zhou, Z. Zhang, C.
Yang, B. Zhang, K. Deng, S. Bottle, H. Zhu, J. Am. Chem. Soc. 2017,
139, 14775-14782.
[4]
[5]
[6]
[7]
a) W. Wu, Chem 2018, 4, 1762-1764; b) M. Hajimohammadi, C.
Schwarzinger, G. Knör, RSC Adv. 2012, 2, 3257-3260.
R. Li, Z. J. Wang, L. Wang, B. C. Ma, S. Ghasimi, H. Lu, K. Landfester,
and K. A. I. Zhang, ACS Catal. 2016, 6, 1113-1121.
G. Jiang, J. Chen, J.-S. Huang, C.-M. Che, Org. Lett. 2009, 11, 4568-
4571.
a) K. Zhang, D. Kopetzki, P. H. Seeberger, M. Antonietti, F. Vilela, Angew.
Chem. Int. Ed. 2013, 52, 1432-1436; b) Z. J. Wang, S. Ghasimi, K.
Landfester, K. A. I. Zhang; Chem. Commun. 2014, 50, 8177-8180; c) Z.
J. Wang, S. Ghasimi, K. Landfester, K. A. I. Zhang, Adv. Mater. 2015,
27, 6265-6270; d) N. Kang, J. H. Park, K. C. Ko, J. Chun, E. Kim, H.-W.
Shin, S. M. Lee, H. J. Kim, T. K. Ahn, J. Y. Lee, S. U. Son, Angew. Chem.
Int. Ed. 2013, 52, 6228-6232.
[8]
J.-X. Jiang, Y. Li, X. Wu, J. Xiao, D. J. Adams, and A. I. Cooper,
Macromolecules 2013, 46, 8779-8783.
This article is protected by copyright. All rights reserved.

10.1002/anie.201811067
Angewandte Chemie International Edition
COMMUNICATION
[9]
W. Wu, D. Mao, F. Hu, S. Xu, C. Chen, C.-J. Zhang, X. Cheng, Y. Yuan,
Wang, X. Han, W. Xi, J. Li, A. W. Roe, P. Lu, J. Qian, Adv. Healthcare
Mater. 2017, 6, 1700685.
D. Ding, D. Kong, B. Liu, Adv. Mater. 2017, 29, 1700548.
[10] a) F. Hu, S. Xu, B. Liu, Adv. Mater. 2018, 30, 1801350; b) W. Fan, P.
Huang, X. Chen, Chem. Soc. Rev. 2016, 45, 6488-6519; c) S. S. Lucky,
K. C. Soo, Y. Zhang, Chem. Rev. 2015, 115, 1990-2042; d) S. Ye, J. Rao,
S. Qiu, J. Zhao, H. He, Z. Y, T. Yang, Y. Deng, H. Ke, H. Yang, Y. Zhao,
Z. Guo, H. Chen, Adv. Mater. 2018, 30, 18011216.
[13] a) S. Xu, Y. Yuan, X. Cai, C.-J. Zhang, F. Hu, J. Liang, G. Zhang, D.
Zhang, B. Liu, Chem. Sci. 2015, 6, 5824-5830; b) W. Wu, D. Mao, S. Xu,
S. Ji, F. Hu, D. Ding, D. Kong, B. Liu, Mater. Horiz. 2017, 4, 1110-1114.
[14] a) H. Uoyama, K. Goushi, K. Shizu, H. Nomura, C. Adachi, Nature 2012,
492, 234-238; b) S. Y. Lee, T. Yasuda, Y. S. Yang, Q. Zhang, C. Adachi,
Angew. Chem. Int. Ed. 2014, 53, 6402-6406.
[11] W.Wu, D. Mao, S. Xu, Kenry, F. Hu, X. Li, D. Kong, B. Liu, Chem 2018,
4, 1937-1951.
[15] T. Werpy, G. Petersen, Top Value Added Chemicals from Biomass,
NREL/TP-510-35523, National Renewable Energy Laboratory, Golden,
CO, 2004.
[12] a) X. Han, Q. Bai, L. Yao, H. C. Liu, Y. Gao, J. Y. Li, L. Q. Liu, Y. L. Liu,
X. X. Li, P. Lu, B. Yang, Adv. Funct. Mater. 2015, 25, 7521-7529; b) Y.
[16] C. Schweitzer, R. Schmid, Chem. Rev. 2003, 103, 1685-1757.
This article is protected by copyright. All rights reserved.

10.1002/anie.201811067
Angewandte Chemie International Edition
COMMUNICATION
Entry for the Table of Contents (Please choose one layout)
Layout 1:
COMMUNICATION
A cross-linked porous conjugated
polymer photosensitizer CPTF was
designed and synthesized for sunlight-
induced photooxidation. Under
simulated AM1.5G irradiation,
Wenbo Wu, Shidang Xu, Guobin Qi,
Han Zhu, Fang Hu, Zitong Liu, Deqing
Zhang, and Bin Liu*
Page No. – Page No.
benzaldehyde can be oxidized to
benzoic acid easily in the scale of 10 g
in the presence of CPTF. In addition,
CPTF can also be used as
A cross-linked conjugated polymer
photosensitizer enables efficient
sunlight-induced photooxidation
photocatalyst for sunlight-induced
organic waste decomposition and
bacterial killing in water.
This article is protected by copyright. All rights reserved.