Available online at www.sciencedirect.
com Current Opinion in
ScienceDirect
Supramolecular artificial light-harvesting systems for
photocatalysis
Kaiya Wang, Yuhong Shen, Ponmani Jeyakkumar,
Yixuan Zhang, Linwang Chu, Rongbo Zhang and Xiao-Yu Hu
Abstract
Photosynthetic organisms are crucial for life as they convert
solar energy into chemical energy, enabling the production of
biomass including food and feed on Earth. Scientists have
been committed to fabricating artificial light-harvesting systems
(ALHSs) in mimicking the process of photosynthesis in nature.
Supramolecular chemistry offers a new strategy for the self-
organization of photosensitive molecules through various
forms of non-covalent interactions. Rapid progress has been
made in constructing supramolecular ALHSs that maximize
the usage of solar sources. Herein, we highlight the repre-
sentative examples for fabricating ALHSs and their applica-
tions for photocatalysis, with an emphasis on these catalyzed
reaction types. The findings presented here will contribute to
the future fabrication of efficient ALHSs as a step towards
understanding natural photosynthesis.
Addresses
College of Materials Science and Technology, Nanjing University of
Aeronautics and Astronautics, Nanjing 211106, China
Corresponding author: Hu, Xiao-Yu (huxy@nuaa.edu.cn)
Current Opinion in Green and Sustainable Chemistry 2023,
41:100823
This review comes from a themed issue on Artificial Photosynthesis
(2023)
Edited by Xiao-Yu Hu and Wanhua Wu
Available online 14 April 2023
For complete overview of the section, please refer the article
collection - Artificial Photosynthesis (2023)
https://doi.org/10.1016/j.cogsc.2023.100823
2452-2236/© 2023 Elsevier B.V. All rights reserved.
Introduction
Photosynthesis is one of the most essential and funda-
mental chemical processes that sustain the function of
the biological system [1]. In green plants, a large number
of antenna pigments (chromophores) are orderly assem-
bled into chloroplasts, which harvest sunlight and transfer
the energy to acceptors, absorb photons via photosyn-
thesis, and react with CO2 and H2O to synthesize organic
compounds. During this process, solar energy is conver-
ted into chemical energy and stored in organic com-
pounds [2,3]. Inspired by the process of photosynthesis,
various kinds of artificial light-harvest systems (ALHSs)
have been developed based on Förster resonance energy
transfer (FRET) to simulate the sunlight-utilizing
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Green and Sustainable Chemistry
process [4]. Nevertheless, the high levels of complexity
and dynamics required for these ALHSs is often difficult
to achieve with pure covalent chemistry [5]. In recent
years, researchers have been concentrating on supramo-
lecular approaches and attempting to construct multi-
functional FRET systems to improve the efficiency of
ALHSs [6e10], and then use the output energy for
photocatalytic reactions [11,12]. The versatile non-
covalent interactions in supramolecular chemistry pro-
vide a simple and effective strategy for ALHSs fabrication
and avoid tedious organic synthesis and purification [13e
16]. Furthermore, one of the most important advantages
of supramolecular assemblies is that the distance and
arrangement between photosensitive molecules can be
regulated to achieve elegant, organized, and sophisticated
microstructures, which ensures the efficiency of ALHSs
and provides venues for photocatalysis.
In order to build efficient FRET-based ALHSs [17],
there are some criteria that deserve our attention.
Firstly, each acceptor requires multiple antenna chro-
mophores (donors) to ensure a high donor/acceptor ratio
just as it occurs in photosynthetic organisms. Secondly,
FRET is a non-radiative energy transfer process through
long-range dipole-dipole interaction between the donor
and acceptor; fluorescence energy transfer from the
donor to the acceptor can be observed only when the
distance between them is appropriate. Thirdly, organic
chromophores are hydrophobic and often suffer from
aggregation-caused quenching (ACQ) effects in the
aqueous phase, resulting in low energy transfer effi-
ciency in water. Benefiting from the aggregation-
induced-emission (AIE) behavior [18e21], many su-
pramolecular AIE-based ALHSs via non-covalent as-
sembly have been fabricated and utilized in various
applications [22e28], among which photocatalysis with
high transformation efficiency is the ultimate goal and
has been customarily explored.
The rapid development of this particular area entails a
deep understanding of molecular recognition and su-
pramolecular assembly. Herein, this minireview sum-
marized the advances made in this field featuring
representative examples over the past two years. The
discussion session was further divided into five different
types of reactions: dehalogenation reaction, cross
dehydrogenative coupling (CDC) reaction, oxidation
reaction, hydrogen evolution reaction, and alkylation
reaction. For comparison, Table 1 listed the five reaction
Current Opinion in Green and Sustainable Chemistry 2023, 41:100823
2 Artificial Photosynthesis (2023)

Table 1

:The representative examples of ALHSs for photocatalysis.

Reaction type FRET step Dye (Acceptor) Donor/acceptor ratio FЕΤ (%) Yield (%) Reference

Dehalogenation reaction One-step ESY 250:1 80.5 55 30

NiR 200:1 60.2 65 30
Two-step (1) ESY 100:1 38.0 – 32
(2) SR101 100:1:0.5 33.0 62–98
(1) ESY 100:1 79.0 – 34
(2) NiR 1000:10:4 79.6 98

Cross dehydrogenative coupling (CDC) reaction One-Step RhB 100:3 56.8 70–90 41
ESY 1:9 43.5 89 44
Two-step (1) ESY 20:1 67.0 – 42
(2) NiR 20:1:0.5 66.0 71–88

Oxidation reaction One-step diiodo-BODIPY 1:1 60.9 >99 47

MB – 78.6 61–85 49
Two-step (1) Coumarin 1:1 86.7 – 46
(2) BODIPY 1:1:1 79.6 –

Hydrogen evolution reaction One-step ESY 10:1 – 62 51

EYB 240:1 96.5 83 52
Two-step (1) CDs 1000:60 84.0 – 53
(2) EY 1000:60:60 76.0 71

Alkylation of C–H bonds Two-step (1) ESY 100:1 28.6 21 54

(2) SR101 500:5:2 59.5 48

that catalyzed by various ALHSs, with an emphasis on Dehalogenation reaction

their donor-to-acceptor ratios, energy transfer effi-
ciencies and yields. We aim to elucidate the significant
role of supramolecular structures in FRET-based
photocatalysis, shedding light on the designing princi-
ple of ALHSs and unveiling the mechanism behind the
complexity of photosynthesis in Nature.
Dehalogenation has attracted significant research in-
terest in realizing the efficient formation of CeH bonds
in organic synthesis. In 2020, our group reported an
ALHS for the photocatalysis of dehalogenation reaction
based on supramolecular assembly [29]. In this study, a
bola-type tetraphenylethylene-functionalized dialkyl

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ammonium derivative (TPEDA) was complexed with
water-soluble pillar[5]arene (WP5), which further
assembled into supramolecular vesicles. Eosin Y (ESY)
was selected as the first energy acceptor, which achieved
efficient energy transfer from the donor (WP5ITPE-
DA assembly). The second acceptor, Nile Red (NiR),
was further encapsulated into the WP5ITPEDA-ESY
assembly, allowing for a two-step sequential energy
transfer process that could be utilized to catalyze the
dehalogenation of a-bromoacetophenone in the aqueous
media. As an extension of the previous work, we recently
reported two highly efficient ALHSs fabricated by WP5,
a bola-type salicylaldehyde-azine derivative (HNPD),
and two hydrophobic fluorescent dyes ESY and NiR
(Figure 1) [30]. ESY or NiR, was entrapped into the
WP5IHNPD assembly, which exhibited a remarkable
emission enhancement and could function as an energy
donor to transfer energy to ESY and NiR, respectively.
With a 250:1 M ratio of the WP5IHNPD assembly to
ESY, the energy transfer efficiency of the
WP5IHNPD-ESY system was calculated to be 80.5%;
Figure 1
Illustration of two supramolecular ALHSs for photocatalysis reported by Hu and Wang’s group, reproduced with permission of ref. 30 from Elsevier.
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Supramolecular photocatalysis Wang et al. 3
while the energy transfer efficiency was calculated to be
60.2% for the WP5IHNPD-NiR system with the
molar ratio of 200:1. In addition, to effectively mimic
natural photosynthesis, the WP5IHNPD-ESY and
WP5IHNPD-NiR supramolecular nanoparticles
served as nanoreactors for the photocatalytic dehaloge-
nation of a-bromoacetophenone in aqueous solution
with moderate yields of 55% and 65%. Based on these
seminal works, various ALHSs constructed by supra-
molecular assembly approaches were employed to
catalyze the dehalogenation reactions, including one-
step and two-step sequential energy transfer [31e39].
Cross dehydrogenative coupling (CDC)
reaction
It is well known that CDC reaction is an effective
method to directly construct CeC bonds from two
different CeH bonds in the presence of oxygen.
Compared with other catalytic methods, CDC reactions
catalyzed by visible light are more environmental
friendly and in compliance with the principle of green
Current Opinion in Green and Sustainable Chemistry 2023, 41:100823
4 Artificial Photosynthesis (2023)
chemistry [40e42]. Yang et al. designed and synthesized
three TPE-branched rotaxane dendrimers (TG1, TG2,
TG3) (Figure 2) as energy donors [43,44]. By selecting
ESY as the receptor, novel ALHSs based on these
rotaxane dendrimers were successfully constructed
through multiple energy transfer processes. At the molar
ratio of 3:1 of TPE to ESY, the energy transfer effi-
ciencies were calculated to be 42.5% for TG1-ESY,
68.2% for TG2-ESY, and 71.6% for TG3-ESY, respec-
tively. These ALHSs are effective photocatalysts for
aerobic CDC reactions; their results suggest that
ALHSs based on higher-generation TPE-branched
rotaxane dendrimers revealed enhanced catalytic per-
formances. The typical cross-coupling of N-phenyl-
1,2,3,4-tetrahydroisoquinoline and indoles was selected
as the model reaction to investigate the catalytic effi-
ciency. By using only 1.0 mol% ALHSs as the catalyst,
Figure 2
Illustration of supramolecular ALHSs for photocatalysis reported by Yang’s group, reproduced with permission of ref. 44 from Wiley.
Current Opinion in Green and Sustainable Chemistry 2023, 41:100823
TG1-ESY achieved complete transformation within
11 h, TG2-ESY within 8 h, and TG3-ESY within 4 h, the
isolated yields were 95%, 90%, and 89%, respectively.
Control experiments using TG1 or ESY alone as catalyst
under the same reaction conditions produced only trace
amounts of transformation, indicating that the synthetic
ALHSs were indeed catalysts. Furthermore, the ALHSs
demonstrated interesting generation-dependent an-
tenna effects. This study herein not only realized the
first successful synthesis of AIEgen-branched rotaxane
dendrimers but also constructed novel ALHSs for
practical applications of CDC photocatalysis.
Oxidation reaction
Recently, ALHS has also been used to catalyze simple
oxidation reactions. Yang et al. reported the supramo-
lecular ALHSs M1 containing precise numbers of
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anthracene, coumarin based on metal ligand coordina-
tion. BODIPY moieties was efficiently incorporated
within M1 through orthogonal self-assembly based on
host guest interactions [45,46]. (Figure 3) Within this
supramolecular system M13L3, anthracene, coumarin,
and BODIPY moieties were precisely distributed,
resulting in a two-step energy transfer from anthracene
to coumarin and then to BODIPY. With a 1:1 M ratio of
L1/L2 in metallacycle M1, the energy transfer effi-
ciency from anthracene to coumarin was calculated to be
86.7% for the one-step FRET process. The results
showed that the energy transfer efficiency of the second
step was calculated to be 79.6% with the molar ratio of
the donor (the host guest complex)/acceptor
(BODIPY) of 1:1:1. The two-step AHLSs exhibited 1.5-
fold higher 1O2 generation efficiency and 1.2-fold higher
photooxidation activity towards sulfide oxidation than
that of its corresponding one-step FRET system.
Although high donor/acceptor ratio is not achieved in
their systems, this study represents the first successful
preparation of multistep FRET systems through
orthogonal coordination-driven self-assembly and
host guest interaction. This same type reaction has also
been catalyzed by Xu’s group using similar
metallacycles-based ALHSs [47]. Moreover, Mukherjee
recently reported three metallasupramolecular cage
based ALHSs for oxidative cyclization with high antenna
Figure 3
Illustration of supramolecular ALHSs for photocatalysis reported by Yang’s group, reproduced with permission of ref. 46 from American Chemical
Society.
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Supramolecular photocatalysis Wang et al. 5
effect and much enhanced yields [48]. A MOF-based
ALHS has also been successfully developed to boost
1
O2 generation and applied towards artemisinin semi-
synthesis [49].
Hydrogen evolution reaction
In 2019, Zhang’s group reported a Pd-cage based ALHS
and applied such system for the cross-coupling hydrogen
evolution reaction for the first time [50]. Later, Liu
et al. reported that a double network phosphorescence
light-harvesting (PLH) supramolecular hydrogel by
assembling the bi-cationic vinyl bromophenyl pyridine
derivative G with cucurbit[8]uril (CB[8]), as well as
acrylamide and hyaluronic acid modified hydroxypropyl-
b-cyclodextrin [51]. In situ copolymerization of G/CB
[8] and acrylamide displayed enhanced phosphores-
cence emission, and co-assembled with b-cyclodextrin
network to achieve a double network PLH (Figure 4).
The phosphorescence lifetime was improved up to
5.17 ms. Owing to the confinement of the system, the
doped ESY acceptor was photosensitized, leading to
efficient energy transfer from triplet phosphors to
singlet acceptors. The delayed fluorescence emission of
ESY was up to 36.4 ms. When the ratio of donor to
acceptor reached 10:1, the energy transfer efficiency was
calculated as 62%. Benefitting from the synergistic
Current Opinion in Green and Sustainable Chemistry 2023, 41:100823
6 Artificial Photosynthesis (2023)

Figure 4

Illustration of supramolecular ALHSs for photocatalysis reported by Liu’s group, reproduced with permission of ref. 51 from Wiley.

Figure 5

Illustration of supramolecular ALHSs for photocatalysis reported by Yi’s group, reproduced with permission of ref. 54 from American Chemical Society.

Current Opinion in Green and Sustainable Chemistry 2023, 41:100823 www.sciencedirect.com


effect of the confined microenvironment and long life-
time photosensitizer, the ALHS was utilized to catalyze
hydrogen evolution reaction, and the yield reached 62%
for photocatalytic reaction in the PLH system. This
study provides a new strategy for the fabrication of
ALHSs based on phosphorescence energy transfer.
Lately, Wang’s group embedded CsPbBr3 quantum dots
into a pillar[5]arene-based supramolecular self-assembly
for the fabrication of ALHS, which showed excellent
photocatalytic activity towards cross-coupling hydrogen
evolution reaction [52]. Liu et al. designed an ALHS
based on dynamic covalent bonded 2D protein nano-
sheets, showing “On/Off ”switchable catalysis for the
same reaction [53].
Alkylation of C–H
Alkylation of CeH bonds is another useful reaction in
organic synthesis. Yi et al. reported a two-step sequen-
tial energy transfer process from M2 assembly to ESY
and then to thiodanamine (SR101), in which a tetrag-
onal platinum (II) metal ring of tetraphenylethylene
(M2) exhibits good AIE effect and serves as a ALHS
platform [54]. (Figure 5) They found that the sequen-
tial energy transfer process can collect and use ultravi-
olet and visible light to activate dyes and enhance light-
trapping systems. With a 100:1 M ratio of the M2 as-
sembly to ESY, the energy transfer efficiency of the M2-
ESY system was calculated to be 28.6% for the first
FRET process. The results showed that the sequential
energy transfer efficiency was calculated to be 59.5%
with the molar ratio of the donor (the M2-ESY assem-
bly)/acceptor (SR101) of 5:2. To better mimic natural
photosynthesis, they found that the M2-ESY-SR101
light-harvesting system facilitates the enhancement of
the photocatalytic activity of CeH chemical bonds
occurring in aqueous solutions. In the presence of
1.0 mol% M2-ESY-SR101 (500:5:2), the conversion of
reactant reached 99%, and the yield reached 48% after
1 h irradiation. Recently, Xing’s group investigated
similar catalytic effects using a polyelectrolyte-based
sequential ALHS [55].
Conclusions
This past two years have witnessed a significant progress
in the realm of supramolecular assembly-based con-
struction of ALHSs, a growing number of which features
high catalytic performance. This review describes the
recent development of these systems for photocatalysis.
ALHSs have been used to catalyze different types of
photocatalytic reactions, such as the dehalogenation
reactions, cross-dehydrogenative coupling reaction,
oxidation, hydrogen evolution reaction, and alkylation
reaction. Despite these fascinating progresses, this field
is still in its infancy, some challenges still lie ahead and
remain to be tackled. First, it is crucial to fabricate
ALHSs with a sequential energy transfer process when
considering that the natural photosynthetic process
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Supramolecular photocatalysis Wang et al. 7
involves multistep sequential rather than a simple one-
step energy transfer. Second, many photocatalytic re-
actions promoted by ALHSs carried out in organic sol-
vents or mixed organic-water solutions, but conducting
reactions in pure water is more economical and
compatible with green chemistry principle. Third, ma-
jority of the reported catalysis is not competitive enough
with natural photosynthesis, or even with other catalytic
methods. The gauge of catalysis is simply compared by
yields, the real kinetics and mechanism behind are
rarely explored. Last, other reaction type such as
asymmetric reaction might be explored in the future,
and potential applications such as biomedical materials
and cell imaging are awaiting to be unveiled. In spite of
these challenges, supramolecular approaches will
certainly disclose more opportunities for ALHSs con-
struction and their practical applications in photosyn-
thesis. We believe that additional studies on ALHSs will
be reported and more types of photocatalytic reactions
will be identified in the future.
Editorial disclosure statement
Given his role as Guest Editor Xiao-Yu Hu, had no
involvement in the peer-review of this article and has no
access to information regarding its peer-review. Full re-
sponsibility for the editorial process for this article was
delegated to Wanhua Wu
Declaration of Competing Interest
The authors declare that they have no known competing
financial interests or personal relationships that could
have appeared to influence the work reported in this
paper.
Data availability
No data was used for the research described in the
article.
Acknowledgments
This work was supported by the National Natural Sci-
ence Foundation of China (Nos. 22271154 and
M 0411), the Natural Science Foundation of Jiangsu
Province (Nos. BK20200432 and BK20211179), and the
Fundamental Research Funds for the Central Univer-
sities (No. NG2022003).
References
Papers of particular interest, published within the period of review,
have been highlighted as:
* of special interest
* * of outstanding interest
1. Qin X, Suga M, Kuang T, Shen JR: Structural basis for energy
transfer pathways in the plant PSI-LHCI supercomplex. Sci-
ence 2015, 348:989–995. https://doi.org/10.1126/
science.aab0214.
2. Romero E, Novoderezhkin VI, van Grondelle R: Quantum design
of photosynthesis for bio-inspired solar-energy conversion.
Nature 2017, 543:355–365. https://doi.org/10.1038/nature22012.
Current Opinion in Green and Sustainable Chemistry 2023, 41:100823
8 Artificial Photosynthesis (2023)
3. Gaut NJ, Adamala KP: Toward artificial photosynthesis. Sci-
ence 2020, 368:587–588. https://doi.org/10.1126/
science.abc1226.
4. Teunissen AJP, Perez-Medina C, Meijerink A, Mulder WJM:
* Investigating supramolecular systems using forster reso-
nance energy transfer. Chem Soc Rev 2018, 47:7027–7044.
https://doi.org/10.1039/c8cs00278a.
This paper details the ways in which FRET has been used to study
non-covalent interactions in both synthetic and biological supramo-
lecular systems.
5. Aratani N, Kim D, Osuka A: Discrete cyclic porphyrin arrays as
artificial light-harvesting antenna. Acc Chem Res 2009, 42:
1922–1934. https://doi.org/10.1021/ar9001697.
6. Peng HQ, Niu LY, Chen YZ, Wu LZ, Tung CH, Yang QZ: Bio-
logical applications of supramolecular assemblies designed
for excitation energy transfer. Chem Rev 2015, 115:
7502–7542. https://doi.org/10.1021/cr5007057.
7. Xiao T, Zhong W, Zhou L, Xu L, Sun X-Q, Elmes RBP, Hu X-Y,
Wang L: Artificial light-harvesting systems fabricated by su-
pramolecular host–guest interactions. Chin Chem Lett 2019,
30:31–36. https://doi.org/10.1016/j.cclet.2018.05.034.
8. Wang K, Velmurugan K, Li B, Hu XY: Artificial light-harvesting
* systems based on macrocycle-assisted supramolecular as-
sembly in aqueous media. Chem Commun 2021, 57:
13641–13654. https://doi.org/10.1039/d1cc06011b.
This review summarizes the recent advances in the preparation of
artificial light-harvesting systems in aqueous solutions.
9. Ahmed S, Kumar A, Mukherjee PS: Tetraphenylethene-based
emissive Pt(II) coordination polymer toward artificial light-
harvesting systems with sequential energy transfer. Chem
Mater 2022, 34:9656–9665. https://doi.org/10.1021/
acs.chemmater.2c02409.
10. Zuo M, Qian W, Hao M, Wang K, Hu X-Y, Wang L: An AIE singlet
oxygen generation system based on supramolecular strat-
egy. Chin Chem Lett 2021, 32:1381–1384. https://doi.org/
10.1016/j.cclet.2020.09.033.
11. Wang K, Jordan JH, Velmurugan K, Tian X, Zuo M, Hu XY,
Wang L: Role of functionalized pillararene architectures in
supramolecular catalysis. Angew Chem Int Ed 2021, 60:
9205–9214. https://doi.org/10.1002/anie.202010150.
12. Wang K, Tian X, Jordan JH, Velmurugan K, Wang L, Hu X-Y: The
emerging applications of pillararene architectures in supra-
molecular catalysis. Chin Chem Lett 2022, 33:89–96. https://
doi.org/10.1016/j.cclet.2021.06.026.
13. Chen XM, Cao KW, Bisoyi HK, Zhang S, Qian N, Guo L, Guo DS,
Yang H, Li Q: Amphiphilicity-controlled polychromatic emis-
sive supramolecular self-assemblies for highly sensitive and
efficient artificial light-harvesting systems. Small 2022, 18,
e2204360. https://doi.org/10.1002/smll.202204360.
14. Li Y, Dong Y, Cheng L, Qin C, Nian H, Zhang H, Yu Y, Cao L:
Aggregation-induced emission and light-harvesting function
of tetraphenylethene-based tetracationic dicyclophane. J Am
Chem Soc 2019, 141:8412–8415. https://doi.org/10.1021/
jacs.9b02617.
15. Dai XY, Huo M, Dong X, Hu YY, Liu Y: Noncovalent
* polymerization-activated ultrastrong near-infrared room-
temperature phosphorescence energy transfer assembly in
aqueous solution. Adv Mater 2022, 34, e2203534. https://
doi.org/10.1002/adma.202203534.
High-efficiency supramolecular phosphorescence-harvesting process
was achieved using noncovalent confinement assembly consisting of
cucurbit[7]uril, b-cyclodextrin and isoquinoline derivatives.
16. Huo M, Dai XY, Liu Y: Ultralarge Stokes shift phosphores-
cence artificial harvesting supramolecular system with near-
infrared emission. Adv Sci 2022, 9, e2201523. https://doi.org/
10.1002/advs.202201523.
17. Acharyya K, Bhattacharyya S, Lu S, Sun Y, Mukherjee PS,
Stang PJ: Emissive platinum(II) macrocycles as tunable
cascade energy transfer scaffolds. Angew Chem Int Ed 2022,
61, e202200715. https://doi.org/10.1002/anie.202200715.
Current Opinion in Green and Sustainable Chemistry 2023, 41:100823
18. Wurthner F: Aggregation-induced emission (AIE): a historical
perspective. Angew Chem Int Ed 2020, 59:14192–14196.
https://doi.org/10.1002/anie.202007525.
19. Zhao Z, Zhang H, Lam JWY, Tang BZ: Aggregation-induced
emission: new vistas at the aggregate level. Angew Chem Int
Ed 2020, 59:9888–9907. https://doi.org/10.1002/
anie.201916729.
20. Qian W, Zuo M, Niu P, Hu XY, Wang L: The construction of
aggregation-induced charge transfer emission systems in
aqueous solution directed by supramolecular strategy. Chin
Chem Lett 2022, 33:1975–1978. https://doi.org/10.1016/
j.cclet.2021.09.070.
21. Wang K, Zuo M, Zhang T, Yue H, Hu XY: Pillar[5]arene–
modified peptide-guanidiniocarbonylpyrrol amphiphiles with
gene transfection properties. Chin Chem Lett 2023, 34,
107848. https://doi.org/10.1016/j.cclet.2022.107848.
22. Tian X, Zuo M, Niu P, Velmurugan K, Wang K, Zhao Y, Wang L,
Hu XY: Orthogonal design of a water-soluble meso-tetra-
phenylethene-functionalized pillar[5]arene with aggregation-
induced emission property and its therapeutic application.
ACS Appl Mater Interfaces 2021, 13:37466–37474. https://
doi.org/10.1021/acsami.1c07106.
23. Xu L, Wang Z, Wang R, Wang L, He X, Jiang H, Tang H, Cao D,
Tang BZ: A conjugated polymeric supramolecular network
with aggregation-induced emission enhancement: an effi-
cient light-harvesting system with an ultrahigh antenna
effect. Angew Chem Int Ed 2020, 59:9908–9913. https://doi.org/
10.1002/anie.201907678.
24. Chen XM, Cao Q, Bisoyi HK, Wang M, Yang H, Li Q: An efficient
near-infrared emissive artificial supramolecular light-
harvesting system for imaging in the golgi apparatus. Angew
Chem Int Ed 2020, 59:10493–10497. https://doi.org/10.1002/
anie.202003427.
25. Yuan YX, Jia JH, Song YP, Ye FY, Zheng YS, Zang SQ: Fluo-
rescent TPE macrocycle relayed light-harvesting system for
bright customized-color circularly polarized luminescence.
J Am Chem Soc 2022, 144:5389–5399. https://doi.org/10.1021/
jacs.1c12767.
26. Qian H, Xiao T, Elmes R, Wang L: Construction of a sequential
light-harvesting system via supramolecular copolymeriza-
tion. Chin Chem Lett 2023. https://doi.org/10.1016/
j.cclet.2023.109195.
27. Zhang X, Wang L, Li N, Xiao Y: Assessing chromatin
condensation for epigenetics with a DNA-targeting sensor by
fret and flim techniques. Chin Chem Lett 2021, 32:2395–2399.
https://doi.org/10.1016/j.cclet.2021.02.031.
28. Luo Y, Zhan W, Ren Q, Chen G, Ran J, Xiao X: A multiple-
function fluorescent pillar[5]arene: Fe3+/Ag+ detection and
light-harvesting system. Chin Chem Lett 2022, 33:5120–5123.
https://doi.org/10.1016/j.cclet.2022.04.028.
29. Hao M, Sun G, Zuo M, Xu Z, Chen Y, Hu XY, Wang L:
* * A supramolecular artificial light-harvesting system with two-
step sequential energy transfer for photochemical catalysis.
Angew Chem Int Ed 2020, 59:10095–10100. https://doi.org/
10.1002/anie.201912654.
An artificial light-harvesting system with a two-step sequential energy-
transfer process in a relay mode was fabricated using a supramolecular
strategy and was used as a nanoreactor for the catalysis of dehalo-
genation reaction for the first time.
30. Sun G, Zuo M, Qian W, Jiao J, Hu X-Y, Wang L: Highly efficient
* artificial light-harvesting systems constructed in aqueous
solution for supramolecular photocatalysis. Green Synth
Catal 2021, 2:32–37. https://doi.org/10.1016/j.gresc.2021.01.003.
Two highly efficient ALHSs were fabricated by WP5, a bola-type sali-
cylaldehyde-azine derivative (HNPD), and two hydrophobic fluorescent
dyes ESY and NiR. The energy transfer efficiency reached 80%.
31. Xing LB, Wang Y, Li XL, Han N, Ma CQ, Liu H, Yu S, Wang R,
Zhuo S: A novel strategy to construct artificial light-
harvesting system based on aggregation-induced emission
surfactants for photocatalysis. Adv Opt Mater 2023, 11,
2201710. https://doi.org/10.1002/adom.202201710.
www.sciencedirect.com

32. Li X-L, Wang Y, Zhang M-H, Jiang M, Liu H, Wang R-Z, Yu S,
Xing L-B: Two-step sequential energy transfer of molecular
assemblies based on host-guest interactions for the con-
struction of photochemically catalyzed artificial light-
harvesting systems. Dyes Pigments 2022, 197, 109895. https://
doi.org/10.1016/j.dyepig.2021.109895.
33. Li X, Wang Y, Song A, Zhang M, Chen M, Jiang M, Yu S, Wang R,
Xing L: An artificial light-harvesting system with tunable
fluorescence color in aqueous sodium dodecyl sulfonate
micellar systems for photochemical catalysis. Chin J Chem
2021, 39:2725–2730. https://doi.org/10.1002/cjoc.202100293.
34. Xiao T, Chen D, Qian H, Shen Y, Zhang L, Li Z-Y, Sun X-Q: Pillar
[5]arene-based light-harvesting assemblies with sequential
energy-transfer for tunable emission and photocatalysis.
Dyes Pigments 2023, 210. https://doi.org/10.1016/
j.dyepig.2022.110958.
35. Wang K, Zhang R, Song Z, Zhang K, Tian X, Pangannaya S,
Zuo M, Hu XY: Dimeric pillar[5]arene as a novel fluorescent
host for controllable fabrication of supramolecular assem-
blies and their photocatalytic applications. Adv Sci 2023,
2206897. https://doi.org/10.1002/advs.202206897.
36. Bai Z, Velmurugan K, Tian X, Zuo M, Wang K, Hu XY: Tetra-
phenylethylene-embedded pillar[5]arene-based orthogonal
self-assembly for efficient photocatalysis in water. Beilstein J
Org Chem 2022, 18:429–437. https://doi.org/10.3762/bjoc.18.45.
37. Jia PP, Hu YX, Peng ZY, Song B, Zeng ZY, Ling QH, Zhao X,
Xu L, Yang HB: Construction of an artificial light-harvesting
system with efficient photocatalytic activity in an aqueous
solution based on a FRET-featuring metallacage. Inorg Chem
2023, 62:1950–1957. https://doi.org/10.1021/
acs.inorgchem.2c01869.
38. Sun G, Cai L, Cui H, Hu Y, Wang J, Wang M, Zhu J, Sun T,
Tang Y: Naphthalenyl-phenylacrylonitrile-based supramolec-
ular aqueous artificial light-harvesting system for photo-
chemical catalysis. Dyes Pigments 2022, 201, 110257. https://
doi.org/10.1016/j.dyepig.2022.110257.
39. Wang Y, Zhu R, Hang Y, Wang R, Dong R, Yu S, Xing L-B:
Artificial supramolecular light-harvesting systems based on
a pyrene derivative for photochemical catalysis. Polym Chem
2023, 14:248–252. https://doi.org/10.1039/d2py01344d.
40. Ma CQ, Han N, Zhang RZ, Wang Y, Dong RZ, Liu H, Wang RZ,
Yu S, Wang YB, Xing LB: Construction of artificial light-
harvesting systems based on a variety of polyelectrolyte
materials and application in photocatalysis. J Colloid Interface
Sci 2022, 634:54–62. https://doi.org/10.1016/j.jcis.2022.11.156.
41. Ma C-Q, Li X-L, Han N, Wang Y, Wang R-Z, Yu S, Wang Y-B,
* Xing L-B: A novel polyelectrolyte-based artificial light-
harvesting system for photocatalysis of cross-
dehydrogenation coupling. J Mater Chem 2022, 10:
16390–16395. https://doi.org/10.1039/d2ta04124c.
This work advances the promising application of artificial light-
harvesting systems based on polyelectrolyte materials for
photocatalysis.
42. Wang Y, Han N, Li XL, Wang RZ, Xing LB: Novel strategy of
constructing artificial light-harvesting system with two-step
sequential energy transfer for efficient photocatalysis in
water. ACS Appl Mater Interfaces 2022, 14:45734–45741.
https://doi.org/10.1021/acsami.2c14168.
43. Li W, Jiang H, Wang X, Zhang D, Zhu Y, Ke Y, Wang W,
Yang HB: Dynamic rotaxane-branched dendrimers with pre-
cisely arranged luminogens for efficient light harvesting.
Mater Today Chem 2022, 24, 100874. https://doi.org/10.1016/
j.mtchem.2022.100874.
44. Li WJ, Wang XQ, Zhang DY, Hu YX, Xu WT, Xu L, Wang W,
* * Yang HB: Artificial light-harvesting systems based on
AIEgen-branched rotaxane dendrimers for efficient photo-
catalysis. Angew Chem Int Ed 2021, 60:18761–18768. https://
doi.org/10.1002/anie.202106035.
www.sciencedirect.com
Supramolecular photocatalysis Wang et al. 9
This is the first successful example of AIEgen-branched dendrimers
that were used to catalyze CDC and oxidation reaction.
45. Huang C, Xu L, Zhu J, Wang Y, Sun B, Li X, Yang HB: Real-Time
monitoring the dynamics of coordination-driven self assem-
bly by fluorescence-resonance energy transfer. J Am Chem
Soc 2017, 139:9459–9462. https://doi.org/10.1021/jacs.7b04659.
46. Jia PP, Xu L, Hu YX, Li WJ, Wang XQ, Ling QH, Shi X, Yin GQ,
* * Li X, Sun H, et al.: Orthogonal self-assembly of a two-step
fluorescence-resonance energy transfer system with
improved photosensitization efficiency and photooxidation
activity. J Am Chem Soc 2021, 143:399–408. https://doi.org/
10.1021/jacs.0c11370.
This study represents the first successful preparation of multistep
FRET systems through orthogonal coordination-driven self-assembly
and host−guest interaction.
47. Jia P, Hu Y, Zeng Z, Wang Y, Song B, Jiang Y, Sun H, Wang M,
Qiu W, Xu L: Construction of FRET-based metallacycles with
efficient photosensitization efficiency and photocatalytic ac-
tivity. Chin Chem Lett 2023, 34, 107511. https://doi.org/10.1016/
j.cclet.2022.05.025.
48. Kumar A, Saha R, Mukherjee PS: Self-assembled metal-
lasupramolecular cages towards light harvesting systems for
oxidative cyclization. Chem Sci 2021, 12:5319–5329. https://
doi.org/10.1039/d1sc00097g.
49. Jiang ZW, Zhao TT, Zhen SJ, Li CM, Li YF, Huang CZ: A 2D
MOF-based artificial light-harvesting system with chloroplast
bionic structure for photochemical catalysis. J Mater Chem
2021, 9:9301–9306. https://doi.org/10.1039/d1ta01278a.
50. Zhang Z, Zhao Z, Hou Y, Wang H, Li X, He G, Zhang M: Aqueous
* platinum(II)-cage-based light-harvesting system for photo-
catalytic cross-coupling hydrogen evolution reaction. Angew
Chem Int Ed 2019, 58:8862–8866. https://doi.org/10.1002/
anie.201904407.
This paper reported a Pd-cage based ALHS and applied such a
system for the cross-coupling hydrogen evolution reaction for the first
time.
51. Yu J, Wang H, Liu Y: Double-network confined supramolecular
* * phosphorescence light-harvesting boosting photocatalysis.
Adv Opt Mater 2022, 10, 2201761. https://doi.org/10.1002/
adom.202201761.
A double network phosphorescence light-harvesting (PLH) supramo-
lecular hydrogel was reported by assembling the bi-cationic vinyl
bromophenyl pyridine derivative G with cucurbit[8]uril, as well as
acrylamide and hyaluronic acid modified hydroxypropyl-b-cyclodextrin.
52. Zhong K, Lu S, Guo W, Su J, Sun S, Hai J, Chen F, Wang A, Wang B:
Embedding CsPbBr3 quantum dots into a pillar[5]arene-based
supramolecular self-assembly for an efficient photocatalytic
cross-coupling hydrogen evolution reaction. J Mater Chem
2021, 9:10180–10185. https://doi.org/10.1039/d1ta00483b.
53. Li Y, Xia C, Tian R, Zhao L, Hou J, Wang J, Luo Q, Xu J, Wang L,
* Hou C, et al.: "On/off" switchable sequential light-harvesting
systems based on controllable protein nanosheets for regu-
lation of photocatalysis. ACS Nano 2022, 16:8012–8021.
https://doi.org/10.1021/acsnano.2c00960.
A controllable protein nanostructure-based “On/Off” switchable ALHS
with sequential multistep energy transfer and photocatalysis was
reported.
54. Zhang D, Yu W, Li S, Xia Y, Li X, Li Y, Yi T: Artificial light-
* * harvesting metallacycle system with sequential energy
transfer for photochemical catalysis. J Am Chem Soc 2021,
143:1313–1317. https://doi.org/10.1021/jacs.0c12522.
This paper reported a two-step sequential energy transfer process, in
which a tetragonal platinum (II) metal ring of tetraphenylethylene ex-
hibits good AIE effect and serves as a ALHS platform.
55. Ma C, Han N, Wang Y, Liu H, Wang R, Yu S, Wang Y, Xing L:
Construction and application of the polyelectrolyte-based
sequential artificial light-harvesting system. Chin Chem Lett
2022. https://doi.org/10.1016/j.cclet.2022.108081.
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