Aqueous Platinum(II)-Cage-Based Light-Harvesting System for Photocatalytic Cross-Coupling Hydrogen Evolution Reaction

Article abstract of DOI:10.1002/anie.201904407

Photosynthesis is a process wherein the chromophores in plants and bacteria absorb light and convert it into chemical energy. To mimic this process, an emissive poly(ethylene glycol)-decorated tetragonal prismatic platinum(II) cage was prepared and used a

Full text of DOI:10.1002/anie.201904407

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Accepted Article
Title: Aqueous Platinum(II) Cage-Based Light-Harvesting System for
Photocatalytic Cross-Coupling Hydrogen Evolution Reaction
Authors: Zeyuan Zhang, Zhengqing Zhao, Yali Hou, Heng Wang,
Xiaopeng Li, Gang He, and Mingming Zhang
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.201904407
Angew. Chem. 10.1002/ange.201904407
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10.1002/anie.201904407
Angewandte Chemie International Edition
DOI: 10.1002/anie.201((will be filled in by the editorial staff))
Light-harvesting
Aqueous Platinum(II) Cage-Based Light-Harvesting System for
Photocatalytic Cross-Coupling Hydrogen Evolution Reaction
Zeyuan Zhang, Zhengqing Zhao, Yali Hou, Heng Wang, Xiaopeng Li, Gang He, Mingming Zhang*
Abstract: Photosynthesis is a process that the chromophores in
plants or bacteria absorb light and covert it to chemical energy. In
order to mimic this process, we prepared an emissive poly(ethylene
glycol)-decorated tetragonal prismatic platinum(II) cage and used it
as the donor molecule to construct a light harvesting system in
water. Eosin Y was chosen as the acceptor due to its good spectral
overlap with the metallacage, which is essential for the prepartion
of light-harvesting systems. Such a combiation showed enhanced
catalytic activity in catalyzing the cross-coupling hydrogen
evolution reaction compared with eosin Y alone. This study offers a
pathway to use the output energy from the light-harvesting systems
to mimic the whole photosynthetic process.
P
hotosynthesis,[1] as the primary source for the fuel on earth, is a
process for living plants or bacteria to absorb, capture, transfer and
store energy from the sun. In this process, the energy from sunlight
is captured and funneled by a dense array of chlorophyll molecules
to the reaction center, and then converted into chemical energy.[2] So
far, plenty of artificial light-harvesting systems mimicking this
process have been developed via a Föster resonance energy transfer
(FRET) process, with the aim to develop clean and sustainable
energy.[3-5] Among them, supramolecular systems[5] have received
considerable attention not only due to their tunable and functionable
molecular structures but also because the energy transfer between
chlorophyll and protein in natural systems also relies on
supramolecular self-assembly. For example, Yang et. al. developed
a highly efficient light-harvesting system based on the self-assembly
of organic nanocrystals.[5b] Wang, Hu and coworkers reported light-
harvesting systems formed by water-soluble pillar[6]arene-based
host-guest interactions.[5g] However, most of these systems just
mimicked the FRET process of natural systems; the use of the
output energy for photocatalytic reactions has been rarely addressed.
As natural photosynthetic systems also use the transferred energy
for chemical reactions, artificial light-harvesting systems with the
ability to catalyze chemical reactions to store and release chemical
energy are urgently needed.
Scheme 1. Self-assembly of metallacages 4a and 4b.
Metal−organic cages or metallacages[6] represent three-
dimensional cage-like structures formed by metal-coordination-
driven self-assembly. With precisely-controlled inner cavities, such
fascinating structures have been widely studied in the past three
decades for guest encapsulation, catalysis and stabilizing reactive
intermediates, etc.[7] Recently, Stang et al. developed a series of
emissive
metallacages[8]
through
the incorporation of
tetraphenylethylene (TPE) derivatives as the building blocks. These
metallacages exhibited aggregation induced emission (AIE)
properties[9] due to the restriction of molecular motions which would
decrease the non-radiative decay. In artificial light-harvesting
systems, thousands of donor molecules are generally used for a
single acceptor, which may cause fluorescence quenching by dye
aggregation. Therefore, the use of AIE-active fluorophores as the
donor molecules offers an alternative strategy to avoid the
fluorescence quenching upon aggregation and increase the
efficiency of ligh-harvesting systems.
[]
Dr. Z. Zhang, Z. Zhao, Y. Hou, Prof. M. Zhang
State Key Laboratory for Mechanical Behavior of Materials, Xi’an
Jiaotong University, Xi’an 710049, P. R. China
E-mail: mingming.zhang@xjtu.edu.cn
Based on the above discussions, it is inferred that the TPE-based
metallacages may behave as good donor molecules for light-
harvesting systems due to their highly emissive and AIE-active
nature. Through the self-assembly of TPE-based sodium benzoate
ligands 1, dipyridyl ligands 2a or 2b and cis-Pt(PEt3)2(OTf)2 3,
metallacages 4a and 4b were prepared in good yields (Scheme 1).
Although the inner framework of the metallacages is hydrophobic,
the introduction of eight poly(ethylene glycol) (PEG) chains affords
metallacage 4b with good solubility in water (>15.0 mM). This
allows us to use it as the donor molecules for the FRET process in
aqueous light-harvesting systems. By the further self-assembly of
Dr. H. Wang, Prof. X. Li
Department of Chemistry, University of South Florida, Tampa,
Florida 33620, United States
Prof. G. He
Frontier Institute of Science and Technology, Xi’an Jiaotong
University, Xi’an 710049, P. R. China
Supporting information for this article is available on the WWW
under http://www.angewandte.org or from the author.
1
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10.1002/anie.201904407
Angewandte Chemie International Edition
spectra of 4a: [M – 5OTf]5+. Partial 1H NMR spectra (400 MHz, CD3COCD3, 295
K) of 2a (e), 4a (f), 2b (g), and 4b (h).
The formation of metallacages 4a and 4b was confirmed by
metallacage 4b with eosin Y which serves as the acceptor molecules
via hydrophobic interactions, an efficient light-harvesting system
was successfully constructed in water. Due to the intense absorption
of 4b in the ultraviolet (UV) region, the light-harvesting system can
not only use the visble light but also exploit the UV light via FRET
to activate eosin Y, making it exhibit enhanced photocatalytic
activity than eosin Y alone. For example, the conversions and yields
increased two-fold in the cross-coupling hydrogen evolution
reaction[10] between benzothiazole and diphenylphosphine oxide
(Scheme 2) upon irradiation by Xe lamp. This study offers an
example where the output energy of a supramolecular light-
harvesting system can be used for chemical synthesis, which is
another step towards artificial photosynthesis.
1
multinuclear NMR spectroscopy (31P{1H} NMR and H NMR) and
electrospray ionization time-of-flight mass spectroscopy (ESI-TOF-
MS). As depicted in Figure 1 (spectra a-c), the 31P{1H} NMR
spectra displayed two doublets of equal intensity with concomitant
195Pt satellites at 5.54 and 0.32 ppm for 4a, 5.45 and 0.31 ppm for
4b, revealing the formation of charge separated metallacages.[8] In
1
the H NMR spectra, significant downfield shifts were observed for
α-pyridyl protons H1 (from 8.61 to 8.92 ppm) and β-pyridyl protons
H2 (from 7.72 to 8.06 ppm) (Figure 1, spectra e and f) as compared
with the free dipyridyl ligand 2a, as a result of the coordination of
the pyridyl moieties to the Pt(II) ions. Analogous downfield shifts
were also observed for metallacage 4b, as α-pyridyl protons H7
shifted from 8.65 to 8.95 ppm and β-pyridyl protons H8 shifted from
7.75 to 8.09 ppm (Figure 1, spectra g and h). Ethoxy protons H4 and
H5 of 4a and H10 and H11 of 4b shifted upfield, which is probably
due to the shielding effect of the cage. ESI-TOF-MS affirmed the
presumptive stoichiometry of metallacage 4a by showing
isotopically well-resolved peaks at m/z = 2407.7954, 1768.7821,
1385.1743, 1129.1058 and 809.5500 (Figure 1d and Supporting
Information, Figure S9), corresponding to [M – 3OTf]3+, [M –
4OTf]4+, [M – 5OTf]5+, [M – 6OTf]6+ and [M – 8OTf]8+,
respectively. Although all the attempts to get the ESI-TOF-MS of
metallacage 4b failed, which is probably due to the polydispersity of
PEG chains along with multiple charge states, we can compare the
1
31P{1H} NMR and H NMR spectra of metallacages 4a and 4b to
Scheme 2. Cartoon representations of the light-harvesting system and its
conclude that both the metallacages were successfully prepared.
application in photocatalytic reaction.
Figure 3. (a) TEM and (b) CLSM images of metallacage 4b in water (c = 10.0
μM, λex = 405 nm). (c) Concentration-dependent optical transmittance at 400 nm
of metallacage 4b in water. Inset: Tyndall effect of metallacage 4b in water (c =
10.0 μM). (d) DLS data of metallacage 4b in water (c = 10.0 μM).
The photophysical properties of metallacages 4a and 4b in
different solvents were collected (Supporting Information, Figure
S12). Both cages show an intense absorption peak centered at ca.
292 nm with a shoulder at 356 nm in almost all the tested solvent,
indicating that the solvents have little influence on the absorption.
Metallacages 4a and 4b are emissive even in dilute solutions
because the metal-coordination bonds restrict the rotation of the
phenyl groups on TPE units,[8] thus decreasing the non-radiative
decay to give bright emission. It is worth noting that metallacage 4b
shows a strong emission peak centered at 511 nm with quantum
yield (Φf) of 23.8% in water. Moreover, similar as previously
Figure 1. Partial 31P {1H} NMR spectra (121.4 MHz, CD3COCD3, 295 K) of 3 (a),
4a (b) and 4b (c). (d) Experimental (red) and calculated (blue) ESI-TOF-MS
2
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10.1002/anie.201904407
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and eosin Y (τ1 = 2.45 ns, τ2 = 5.69 ns) was shorter than that of 4b
(τ1 = 2.76 ns, τ2 = 6.30 ns), giving another evidence for the efficient
energy transfer from metallacage 4b to eosin Y.[5] When the molar
ratio of 4b/eosin Y is 20, the energy transfer efficiency reached 45%,
which is comparable to previously reported supramolecular light-
harvesting systems in aqueous solution.[5g]
reported TPE-based metallacages,[8] it is also AIE-active
(Supporting Information, Figure S12). These characteristics make it
a good energy donor for aqueous light-harvesting systems.
The self-assemblies formed by metallacage 4b in water were
studied by transmission electron microscopy (TEM), confocal laser
scanning microscopy (CLSM) and dynamic light scattering (DLS)
measurements. It can be seen clearly that metallacage 4b forms
spherical micelles with an average diameter of 140 nm at 10.0 μM
(Figure 3a). Moreover, because metallacage 4b is emissive in water,
nanoparticles with bright emission and diameter of 190 nm were
visualized by CLSM (Figure 3b). The critical aggregation
concentration (CAC) of metallacage 4b was measured to be 8.83 ×
10-6 M by plotting the optical transmittance versus the concentration
of 4b at 400 nm (Figures 3c and Supporting Information, Figure
S13). DLS measurements showed that metallacage 4b formed large-
sized aggregates with averaged hydrodynamic diameters (Dh) of 185
nm (Figure 3d), consistent with the TEM and CLSM results. In the
micelles, the hydrophobic inner frameworks of metallacage 4b form
the core and the PEG chains form the corona, which further
assembled into spherical nanoparticles via hydrophobic interactions
(Scheme 2).
Figure 5. (a) Conversions of compound 5 versus reaction time. (b) Yields of
compound 7 versus reaction time. (c) Plausible mechanism of cross-coupling
hydrogen evolution reaction using LHS as photocatalyst. LHS = light-harvesting
system.
It is known that eosin Y can be used as a photosensitizer to
catalyze C–H arylation of heteroarenes and cross-coupling hydrogen
evolution reactions.[10] In order to use the output energy to mimick
the whole photosynthetic process, we employed the above light-
harvesting system as a photocatalyst for cross-coupling reaction
between benzothiazole 5 and diphenylphosphine oxide 6 in water.
For eosin Y-based photocatalytic reactions, green light or visible
light is generally used as the light source[10b] because eosin Y shows
little absorption in the UV region. However, in our system, because
metallacage 4b exhibits strong absorption in the UV region, it can
serve as an antenna to transfer the energy from the UV light to eosin
Y, indicating that we can directly use solar light (Here we used Xe
lamp as the solar light simulator) to trigger the photocatalytic
reaction. As shown in Figures 5a and 5b, both the coversions of
compound 5 and the yields of compound 7 increased dramatically
by using the light-harvesting system compared with eosin Y alone.
After 12 h of reaction, the coversion of 5 reached 88% and the yield
of 7 reached 65% while the light-harvesting system was used as the
photocatalyst, compared with that only 40% coversion and 33%
yield were obtained by eosin Y alone. Nearly no catalytic activity
was observed for metallacage 4b. The FRET process increases the
number of excitated photocatalyst (eosin Y*), which will undergo to
the catalytic cycle (Figure 5c) to increase the catalytic activity.
Meanwhile, hydrogen was produced by the combination of
dissociated hydrogen radicals, offering a pathway to store the energy
from the light. Moreover, the photobleaching effect of eosin Y upon
Figure 4. (a) Normalized absorption spectrum of eosin
Y and emission
spectrum of 4b. (b) Fluorescence spectra of 4b (c = 30.0 µM) in water with
different concentrations of eosin Y (λex = 365 nm). (c) CLSM image of 4b (c =
10.0 µM) and Eosin Y (c = 5.0 µM) in water (λex = 405 nm). (d) Fluorescence
decay profiles of 4b (blank line), 4b and eosin Y (red line). ([4b] = 30.0 µM,
[eosin Y] = 1.6 µM).
Eosin Y was used as the acceptors for metallacage 4b to construct
an aqueous light-harvesting system because the absorption of eosin
Y overlaps well with the emission of metallacage 4b in water
(Figure 4a). With the gradual addition of eosin Y to the aqueous
solution of metallacage 4b, the emission intensity at 511 nm derived
from metallacage 4b decreased, while a new emission band at 550
nm ascribed to eosin Y appeared and increased when excited at 365
nm (Figure 4b). These phenomena suggested that efficient energy
transfer took place from metallacage 4b to eosin Y. This process
was also evidenced by the images taken by CLSM. When the light-
harvesting system was irradiated at 405 nm, a FRET process took
place from metallacage 4b to eosin Y, therefore some red
nanopartciles derived from eosin Y were observed even though
eosin Y itself can not be excited at 405 nm (Figure 4c and
Supporting information, Figure S14). The fluorescence decay
measurements were also carried out to study the light-harvesting
process. The fluorescence lifetime (τ) of the assembly formed by 4b
3
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10.1002/anie.201904407
Angewandte Chemie International Edition
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In summary, two TPE-based tetragonal prismatic platinum (II)
cages were prepared and characterized by 31P NMR, 1H NMR, ESI-
TOF-MS, UV absorption and fluorescence spectroscopy. Through
the incorporation of PEG chanis on the pillar parts of the
metallacage, it exhibits good water-solubility and is highly emissive
in water. The metallacage was further used as energy donor for
eosin Y to prepare an efficient light-harvesting system in water via a
FRET process. More importantly, the light-harvesting system shows
good photocatalytic activity for cross-coupling hydrogen evolution
reaction, offering the products in the yields almost two-fold of eosin
Y alone. This study not only gives a type of metallacage-based
structures as energy donors for the construction of efficent light-
harvesting systems, but also utilizes the output energy for
photocatalytic reactions to prepare useful hydrocarbons and release
gas, which will pave the way for the fabrication of artificial
photosynthetic systems.
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Acknowledgements
This work was supported by the National Natural Science
Foundation of China (21801203 to M. Z.), National Science
Foundation (CHE-1506722 to X. L.), National Institutes of Health
(R01GM128037 to X. L.). M. Z. is thankful for start-up funds from
Xi’an Jiaotong University. We thank Dr. Gang Chang and Yu Wang
at Instrument Analysis Center and Dr. Aqun Zheng and Junjie
Zhang at Experimental Chemistry Center of Xi’an Jiaotong
University for NMR and fluorescence measurements.
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Published online on ((will be filled in by the editorial staff))
Keywords: supramolecular chemistry · metallacage · light-
harvesting · photocatalysis · cross-coupling hydrogen evolution
reaction
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4
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Angewandte Chemie International Edition
COMMUNICATION
Zeyuan Zhang, Zhengqing Zhao, Yali
Hou, Heng Wang, Xiaopeng Li, Gang
He, Mingming Zhang*
Page No. – Page No.
Aqueous Platinum(II) Cage-Based
Light-Harvesting
Photocatalytic
System
Cross-Coupling
for
Hydrogen Evolution Reaction
An aqueous light-harvesting system with efficient energy transfer based on platinum(II) cage and eosin Y was developed. The
system showed improved photocatalytic activity in the cross-coupling hydrogen evolution reaction compared with eosin Y alone.
5
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