Artificial Light-Harvesting Metallacycle System with Sequential Energy Transfer for Photochemical Catalysis

Article abstract of DOI:10.1021/jacs.0c12522

Highly efficient light-harvesting systems with the sequential energy transfer process are significant for utilizing solar energy in photosynthesis. Herein, we report a quadrilateral platinum(II) metallacycle containing tetraphenylethylene (M1) as a light-

Full text of DOI:10.1021/jacs.0c12522

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Artificial Light-Harvesting Metallacycle System with Sequential
Energy Transfer for Photochemical Catalysis
Dengqing Zhang,* Wei Yu, Suwan Li, Yan Xia, Xianying Li, Yiran Li, and Tao Yi*
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ABSTRACT: Highly efficient light-harvesting systems with the sequential energy transfer process are significant for utilizing solar
energy in photosynthesis. Herein, we report a quadrilateral platinum(II) metallacycle containing tetraphenylethylene (M1) as a light-
harvesting platform. The M1 assembly serves as an ideal donor because of the aggregation-induced emission (AIE) effect, realizing
two-step sequential energy transfer from the M1 assembly to eosin Y (ESY) and then to sulforhodamine (SR101) with high
efficiency. ESY was used as a bridge in a relay mode during this process. To better mimic natural photosynthesis, the M1−ESY−
SR101 system was utilized as photochemical catalysis for alkylation of C−H bonds in aqueous solution, showing enhanced catalytic
activity as compared with the M1−ESY system or ESY/SR101 alone.
Herein, we synthesized a quadrilateral platinum(II) metal-
lacycle containing tetraphenylethylene (M1) (Scheme 1).
ight-harvesting systems (LHSs) have inspired consider-
Lable research interests on account of their important roles
in photosynthesis.1 In nature, multiple close-packed antenna
chromophores (donors) harvest sunlight and funnel the
collected energy to one acceptor. A variety of platforms such
as polymers,2 metal−organic frameworks,3 dendrimers,4 supra-
molecular systems,5 nanocrystals,6 and DNA7 have been
successfully developed to mimic natural LHSs. These platforms
were generally classified into two categories: covalent systems
and noncovalent systems. The first category showed
remarkable stability but contained limited donor chromo-
phores per acceptor because of synthetic difficulties. In
contrast, the second one possessed controllable and dynamic
components and facilitated adjustment of donor−acceptor
ratios. Therefore, supramolecular coordination complexes with
AIE features could be ideal platforms for constructing LHSs.
Recently, the well-defined metallacycles/cages with easy
synthetic accessibility and AIE properties have been reported
for chemical sensing,8 holographic storage,9 and biomedical
diagnosis,10 but the application in LHSs is still limited. Stang et
al. reported LHSs based on fluorescent hexagonal Pt(II)
metallacycles.11 Cao and co-workers reported two tetraphenyl-
ethylene-based supramolecular coordination frameworks for
light harvesting.12 Zhang and co-workers fabricated LHSs
based on tetragonal prismatic platinum(II) cages.13 However,
these works focused on only one-step energy transfer, while the
natural LHSs are characterized by sequential energy transfer
(SET).14 The SET could achieve a larger Stokes shift and more
effective energy transfer between initial donor and final
acceptor fluorophores even in the absence of any spectral
Scheme 1. Self-Assembly of Metallacycle M1 and Chemical
Structure of Organic Macrocycle M2
Benefiting from the AIE characteristic, M1 is a remarkable
donor chromophore in LHS. Eosin Y (ESY), which can insert
into the hydrophobic core of M1 assembly, is loaded as the
first acceptor of the LHS. Subsequently, with ESY as a relay
and sulforhodamine (SR101) as the second energy acceptor,
two-step SET process can be realized from M1 assembly to
ESY and then to SR101 (Scheme 2). Because the two-step
Received: December 1, 2020
Published: January 15, 2021
̈
overlap and/or beyond the Forster radius. Until now, only a
few LHSs with the SET process have been developed.15 To our
knowledge, the LHSs with SET based on metallacycles have
not been reported. Furthermore, the utilization of harvested
light energy by artificial LHSs for photocatalytic reaction
remains less addressed.
https://dx.doi.org/10.1021/jacs.0c12522
J. Am. Chem. Soc. 2021, 143, 1313−1317
© 2021 American Chemical Society
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Journal of the American Chemical Society
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Communication
M1 in the methanol solution was very weak but became
stronger in the solid state (quantum yield: 18.80%), indicating
good AIE character. With the increase of water fractions (fw)
in the methanol solution of M1, the fluorescence intensity
gradually increased (Figure S28). When fw reaches 30%, the
highest fluorescence intensity was observed, while a further
increase of fw resulted in a decrease of fluorescence intensity.
At fw = 95%, the fluorescence intensity was reduced by about
40%, possibly because of the formation of less emissive
nanoaggregates by random molecular packing.17 However, to
better mimic the processes of natural LHS working in an
aqueous environment, fw = 95% was chosen in the following
experiment.
Scheme 2. Illustration of the Construction of the
Metallacycle-Based LHS and the Process of Light
Harvesting
The morphology of the assemblies formed by M1 in H2O−
CH3OH (19:1; v/v) was investigated by TEM and SEM,
which suggested the formation of nanospheres (Figure 2a and
SET process can not only utilize ultraviolet light but also use
visible light to activate dyes, the LHS based on metallacycle
M1 exhibited enhanced photocatalytic activity. For compar-
ison, organic macrocycle M2 was also synthesized as a
reference compound (Scheme 1).
The quadrilateral [2 + 2] metallacycle M1 was synthesized
by coordination-driven self-assembly of TPE-based donor 3
and diplatinum(II) acceptor 4 in good yield (Scheme 1). The
1
structure of M1 was confirmed by H NMR, 31P{1H} NMR,
and ESI-TOF-MS (Figure 1 and Figures S14−S16). As
Figure 2. TEM images of the assemblies of M1 (a), M1−ESY (b),
and M1−ESY−SR101 (c). DLS profiles of the assemblies of M1 (d),
M1−ESY (e), and M1−ESY−SR101 (f). Inset: the Tyndall effect.
[M1] = 1.0 μM, [ESY] = 0.01 μM, and [SR101] = 0.004 μM.
Figure S29a). The average hydrodynamic diameter of M1
assemblies was found to be 214 nm by dynamic light scattering
(DLS) measurement (Figure 2d). In addition, M1 showed a
noticeable Tyndall effect in aqueous solution (inset of Figure
2d), suggesting the existence of aggregates. An average ζ-
potential of M1 assembly is +2.87 mV (Figure S30), exhibiting
that the surfaces of nanospheres were covered by the positive
charge.
On the basis of the above results, we expected that M1 could
act as a suitable donor in LHS. The emission of M1 assembly
matched well with the absorption of ESY (Figure S31);
therefore, ESY was chosen as the first acceptor. As depicted in
Figure 3a, with the addition of ESY into the M1 assembly, the
emission intensity of ESY (acceptor) at 555 nm progressively
increased along with the decrease of M1 (donor) emission at
495 nm when excited at 370 nm in H2O−CH3OH (19:1; v/v).
In control experiments, the emission of ESY was negligible
without M1 antenna under the same conditions (Figure S32),
excluding the probability of direct excitation of ESY. The
corresponding fluorescent color changed from green of the M1
assembly to yellow-green of the M1−ESY system (Figure
2d,e), clearly demonstrating the efficient energy transfer from
the M1 assembly to ESY. Furthermore, the average diameter of
the M1−ESY assembly had a slight increase (Figure 2b,e).
Subsequently, the fluorescence decay experiment showed that
the lifetimes decreased from the M1 assembly (τ1 = 1.36 ns, τ2
= 3.59 ns) to the M1−ESY assembly (τ1 = 0.87 ns, τ2 = 2.90
ns) (Figure 3b and Table S1), indicating that the harvested
energy by M1 was successfully transferred to ESY. In the M1−
ESY system, the energy transfer efficiency (ΦET) reached
Figure 1. Partial 31P {1H} NMR spectra (121.4 MHz, CD2Cl2, 295 K)
of 4 (a) and M1 (b). Partial H NMR spectra (400 MHz, CD2Cl2,
1
295 K) of 3 (c) and M1 (d). (e) Calculated (red) and experimental
(blue) ESI-TOF-MS spectra of M1: [M-3OTf]3+.
depicted in Figure 1, the 31P{1H} NMR spectrum of M1
shifts upfield compared with that of 4 and displays a sharp
singlet peak at δ = −3.14 ppm (Figure 1b) with concomitant
195Pt satellites at δ = 6.53 and −12.72 ppm, revealing the
formation of highly symmetric structure. Compared with the
free ligand 3, the pyridyl proton signals of metallacycle M1
showed significant downfield shifts (Hα: from δ = 8.60 to 9.06
ppm; Hβ: from δ = 7.32 to 7.74 ppm) in the 1H NMR spectra
(Figure 1c,d) because of the formation of Pt−N bonds. The
mass spectrum of M1 showed a peak at m/z 1161.53,
corresponding to [M-3OTf]3+, matched well with its
theoretical isotopic resolution patterns (Figure 1e). The
organic macrocycle M2 was synthesized according to our
previous report.16
The TPE-based metallacycle M1 has good solubility in
methanol and is almost insoluble in water. The fluorescence of
1314
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Communication
shortened, which guaranteed efficient energy transfer.
Compared with M1, the interaction between the neutral
organic macrocycle M2 and ESY/SR101 was weaker, resulting
in the inefficient FRET process. Furthermore, the M2 assembly
precipitated within 2 h, while the M1 assembly remained stable
at least 72 h at room temperature, indicating that the
electrostatic repulsive forces among nanospheres induced by
positively charge can prevent their agglomeration and promote
their stability in aqueous solution.5g,12,15b,d
Subsequently, the M1−ESY−SR101 system was utilized as
photocatalyst to catalyze the alkylation of C−H bonds in an
aqueous medium. Because M1 has strong absorption in the UV
region, M1 can function as an antenna to absorb UV light and
funnel the collected energy to organic dyes through sequential
FRET process. Hence, the sunlight can be directly utilized.
The photochemical reaction of phenyl vinyl sulfone and
tetrahydrofuran was chosen as an example (Xe lamp as sunlight
Figure 3. Emission spectra of M1 with different amounts of ESY (a)
and M1−ESY (100:1) with different amounts of SR101 (c) in H2O−
CH3OH (19:1; v/v) (λex = 370 nm). The fluorescence lifetime of M1
and M1−ESY (100:1) monitored at λ = 495 nm (b) and M1−ESY
(100:1) and M1−ESY−SR101 (500:5:2) monitored at λ = 555 nm
(d) in H2O−CH3OH (19:1; v/v).
simulator).19 The reaction process was followed by H NMR
1
28.6% at the donor/acceptor ratio of 100:1 in H2O−CH3OH
(19:1; v/v) (Table S2). The antenna effect (AE) was 18.3
(Table S5), and the fluorescence quantum yield was 19.31%
(Table S3) under the same conditions.
spectra (Figure S46), and the product was isolated and purified
by column chromatography on silica gel. As shown in Table 1
Table 1. Photocatalytic Alkylation of C−H Bonds
Given that the natural photosynthesis process is charac-
terized by the SET, we decided to construct a SET system by
using metallacycle M1. Because the absorption spectrum of
SR101 and the emission spectrum of the M1−ESY assembly
were well overlapped (Figure S39), SR101 was chosen as the
energy acceptor. With the addition of SR101 into the M1−ESY
system, the emission band at 607 nm ascribed to SR101
gradually increased, while the emission peak of ESY at 555 nm
decreased (Figure 3c), accompanied by the visual fluorescent
color changes from yellow-green to light red (Figure 2e,f). The
average diameter of the M1−ESY−SR101 assembly was larger
than that of the M1−ESY assembly (Figure 2c,f).18 In the
M1−ESY−SR101 system, the fluorescence quantum yield, the
second-step energy transfer efficiency, and the second-step
antenna effect were determined to be 24.06%, 59.5%, and 8.9,
respectively (Figures S42 and S43, Tables S3−S5) at the
M1:ESY:SR101 ratio of 500:5:2. The fluorescence decay
experiments showed a decline of the fluorescence lifetime from
the M1−ESY assembly (τ1 = 2.20 ns, τ2 = 3.74 ns) to the M1−
ESY−SR101 assembly (τ1 = 1.75 ns, τ2 = 3.55 ns) (Figure 3d
and Table S1). The above results indicated that the M1
assembly successfully served as a donor in LHS, the two-step
SET took place from the metallacycle to ESY, and then SR101
in the relay mode.
Furthermore, the organic macrocycle M2 was also utilized as
an energy donor to build LHS. As a result, the one-step energy
transfer from the M2 assembly to ESY was realized (Figure
S44a). However, the SET process was inconspicuous after the
further introducing of SR101 into the M2−ESY assembly
(Figure S44b), although the emission band of M2−ESY
assembly was overlapped with the absorption band of SR101
(Figure S45). On the basis of the above experimental results,
we speculate that ESY and SR101 can be inserted into the
hydrophobic core of M1 assembly through the hydrophobic
effect, π−π interactions, and electrostatic interactions. The
distance between M1 and ESY/SR101 is significantly
a
entry
conditions
light irradiation conv [%]
yield [%]
1
2
3
4
5
M1
yes
yes
yes
yes
no
85
99
85
99
10
8
27
21
48
ESY/SR101
M1−ESY
M1−ESY−SR101
M1−ESY−SR101
no reaction
a
Isolated yields.
and Figure S48, in the presence of 1 mol % M1−ESY−SR101
(500:5:2), the conversion of 12 reached 99%, and the yield of
13 reached 48% after 1 h irradiation in H2O−THF (19:1; v/
v). In contrast, only 85% conversion and 21% yield were
obtained by using the M1−ESY system. The lowest yield was
obtained for M1 as photocatalyst. Furthermore, there was
almost no catalytic activity in the absence of light. The M1−
ESY−SR101 system as photocatalyst not only significantly
shortened the reaction time but also successfully realized the
functionalization of C−H bonds in aqueous solution. Three
possible factors contribute to the excellent photocatalytic
efficiency of the M1−ESY−SR101 system: (I) The AIE
property of M1 can effectively prevent fluorescence self-
quenching, which makes M1 an ideal donor in LHS. (II) The
two-step SET of the M1−ESY−SR101 system could enhance
the utilization of UV light from the solar energy spectrum and
increase the light-use efficiency. (III) The photobleaching was
reduced, and the distance between donors and acceptors was
shortened on account of loading the ESR/SR101 into the
hydrophobic layer of nanospheres. These results demonstrated
that the M1−ESY−SR101 system could take full advantage of
the collected solar energy to effectively catalyze the photo-
chemical reaction in the aqueous phase, which provides a new
strategy to improve the photocatalytic activities of the
photosensitizers.
In summary, an efficient LHS with a two-step SET process
was successfully fabricated based on an AIE-active quadrilateral
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metallacycle. The AIE-active M1 assembly served as an ideal
energy donor; after ESY was introduced as energy acceptor, the
first-step energy transfer process occurred. Subsequently, with
ESY as a relay and SR101 as the second energy acceptor, two-
step SET process was successfully realized in aqueous medium.
Furthermore, the M1−ESY−SR101 LHS showed good
photocatalytic activity for alkylation of C−H bonds in aqueous
solution. Therefore, the artificial sequential LHS based on the
metallacycle M1 indicated potential applications in mimicking
natural photosynthesis.
ASSOCIATED CONTENT
* Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/jacs.0c12522.
■
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Syntheses and characterization data of all new
compounds; other experimental details (PDF)
AUTHOR INFORMATION
Corresponding Authors
■
Dengqing Zhang − State Key Laboratory for Modification of
Chemical Fibers and Polymer Materials, College of
Chemistry, Chemical Engineering and Biotechnology,
Donghua University, Shanghai 201620, China; orcid.org/
0000-0003-1551-7160; Email: dqzhang@dhu.edu.cn
Tao Yi − State Key Laboratory for Modification of Chemical
Fibers and Polymer Materials, College of Chemistry,
Chemical Engineering and Biotechnology, Donghua
University, Shanghai 201620, China; Email: yitao@
dhu.edu.cn
(3) (a) Williams, D. E.; Rietman, J. A.; Maier, J. M.; Tan, R.;
Greytak, A. B.; Smith, M. D.; Krause, J. A.; Shustova, N. B. Energy
Transfer on Demand: Photoswitch-Directed Behavior of Metal−
Porphyrin Frameworks. J. Am. Chem. Soc. 2014, 136, 11886−11889.
(b) Yu, J.; Anderson, R.; Li, X.; Xu, W.; Goswami, S.; Rajasree, S. S.;
Authors
Wei Yu − State Key Laboratory for Modification of Chemical
Fibers and Polymer Materials, College of Chemistry,
Chemical Engineering and Biotechnology, Donghua
University, Shanghai 201620, China
Suwan Li − State Key Laboratory for Modification of Chemical
Fibers and Polymer Materials, College of Chemistry,
Chemical Engineering and Biotechnology, Donghua
University, Shanghai 201620, China
Yan Xia − State Key Laboratory for Modification of Chemical
Fibers and Polymer Materials, College of Chemistry,
Chemical Engineering and Biotechnology, Donghua
University, Shanghai 201620, China
Xianying Li − School of Environmental Science and
Engineering, Donghua University, Shanghai 201620, China
Yiran Li − Department of Chemistry, Fudan University,
Shanghai 200433, China
́
́
Maindan, K.; Gomez-Gualdron, D. A.; Deria, P. Improving Energy
Transfer within Metal-Organic Frameworks by Aligning Linker
Transition Dipoles along the Framework Axis. J. Am. Chem. Soc.
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Mondloch, J. E.; Hupp, J. T.; Farha, O. K. Metal-Organic Framework
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M.; Fan, Y.; Guo, J.; Shi, J.; Su, C. A Metal-Organic Cage
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Complete contact information is available at:
https://pubs.acs.org/10.1021/jacs.0c12522
(5) (a) Peng, H.; Niu, L.; Chen, Y.; Wu, L.; Tung, C.; Yang, Q.
Biological Applications of Supramolecular Assemblies Designed for
Excitation Energy Transfer. Chem. Rev. 2015, 115, 7502−7542.
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Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
This work was supported by the National Natural Science
Foundation of China (21672036) and the Natural Science
Foundation of Shanghai (18ZR1400900).
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