Highly Efficient Artificial Light-Harvesting Systems Constructed in Aqueous Solution Based on Supramolecular Self-Assembly

Article abstract of DOI:10.1002/anie.201800175

Highly efficient light-harvesting systems were successfully fabricated in aqueous solution based on the supramolecular self-assembly of a water-soluble pillar[6]arene (WP6), a salicylaldehyde azine derivative (G), and two different fluorescence dyes, Nile

Full text of DOI:10.1002/anie.201800175

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Accepted Article
Title: Highly Efficient Artificial Light-Harvesting Systems Constructed in
Aqueous Solution Based on Supramolecular Self-Assembly
Authors: Shuwen Guo, Yongshang Song, Yuling He, Xiao-Yu Hu, and
Leyong Wang
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.201800175
Angew. Chem. 10.1002/ange.201800175
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Highly Efficient Artificial Light-Harvesting Systems Constructed
in Aqueous Solution Based on Supramolecular Self-Assembly
Shuwen Guo, Yongshang Song, Yuling He, Xiao-Yu Hu,* and Leyong Wang*
Abstract: Highly efficient light-harvesting systems are successfully
fabricated in aqueous solution based on the supramolecular self-
assembly of a water-soluble pillar[6]arene (WP6), a salicylaldehyde
azine derivative (G), and two different fluorescence dyes, nile red
(NiR) or eosin Y (ESY). The WP6-G supramolecular assembly
exhibits remarkably improved aggregation-induced emission
enhancement and acts as a donor for the artificial light-harvesting
system, and NiR (or ESY) which is loaded within the WP6-G
assembly acts as different acceptors. Notably, efficient energy-
transfer process takes place from the WP6-G assembly not only to
NiR but also to ESY for these two different systems. Furthermore,
both of the WP6-G-NiR and WP6-G-ESY systems show ultrahigh
antenna effect at a high donor/acceptor ratio.
harvesting systems constructed based on covalent bonds (such
as porphyrin arrays and dendrimers) always faced multistep
synthesis difficulties,[5] which hampered their scale up and
widespread application. Whereas, supramolecular self-assembly
paves a promising and facile way for constructing artificial light-
harvesting systems. In fact, a variety of artificial light-harvesting
systems have been successfully constructed via non-covalent
assembly, including supramolecular polymers,[6] organogels,[7]
biomaterials,[8] and organic–inorganic hybrid materials.[9]
However, most of these reported artificial light-harvesting
systems were fabricated in organic solvents instead of the
aqueous environment like in nature. Since the donor
chromophores are generally hydrophobic and exhibit undesired
aggregation-caused quenching (ACQ) effect, they always show
very poor energy transfer efficiency in water.[10] Up to now, only
a few examples of efficient aqueous light-harvesting systems
have been delicately fabricated to address this problem. For
examples, Zhou and coworkers designed pomegranate-like
unimolecular micelle aggregates with porphyrin core structure to
effectively inhibit the self-quenching between porphyrin
Photosynthesis is the survival foundation for living creatures,
during its primary process, sunlight is captured, transferred, and
stored as chemical energy.[1] This process takes place in
chloroplast pigments with highly efficient photon-harvesting
owing to the large number of closely packed chlorophylls within
the pigment-protein complexes. Subsequently, excitation energy
migrates among chlorophyll molecules, which is finally
transferred to the reaction center, where the excitation energy is
converted into chemical energy.[2] The large number of closely
packed antenna pigments (ca.200) around the reaction center is
one of the most remarkable features for natural harvesting
systems, which helps organisms thrive even under the extremely
low-light conditions.[3] Inspired by nature, up to now, great
progress has been made in mimicking natural light-harvesting
process by achieving efficient energy transfer from donors to
acceptors through a Förster resonance energy transfer (FRET)
process.[4] In order to fabricate an artificial light-harvesting
system with high energy collection efficiency, there are two key
factors that should be taken into account: (1) the system should
contain multiple donors per acceptor; (2) the donor should be
closely packed but without intramolecular fluorescence self-
quenching. In nature, green plants rely on non-covalent self-
assembly between chlorophyll and protein to form the efficient
light-harvesting antenna. So far, the reported artificial light-
chromophores.[3c]
Liu
and
coworkers
exploited
an
oligo(phenylenevinylene) derivative to serve as an idea donor,[3b]
which exhibited the aggregation-induced emission but without
the undesired ACQ effect. Therefore, it is still a very challenging
task to design and fabricate highly efficient light-harvesting
systems in aqueous environment.
Herein, we report two novel aqueous light-harvesting systems
which are fabricated based on the supramolecular self-assembly
[*]
S. Guo, Y. Song, Dr. X.-Y. Hu, Prof. Dr. L. Wang
Key Laboratory of Mesoscopic Chemistry of MOE and Collaborative
Innovation Center of Chemistry for Life Sciences, School of
Chemistry and Chemical Engineering, Nanjing University, Nanjing
210023, China.
E-mail: lywang@nju.edu.cn (LW); huxy@nju.edu.cn (XH).
Y. He
State Key Laboratory of Analytical Chemistry for Life Science,
Collaborative Innovation of Chemistry for Life Science, School of
Chemistry and Chemical Engineering, Nanjing University, Nanjing
210023, China.
Prof. Dr. L. Wang
School of Petrochemical Engineering, Changzhou University,
Changzhou, 213164, China.
Scheme 1. Schematic illustration of the self-assembly of pillar[6]arene-based
Supporting information for this article is given via a link at the end of
the document.
aqueous light-harvesting systems.
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10.1002/anie.201800175
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of a water-soluble pillar[6]arene (WP6), a salicylaldehyde azine
derivatives (G), and two different fluorescence dyes, nile red
(NiR) or eosin Y (ESY). Since the salicylaldehyde azine
derivatives are highly emissive in aggregates through the
combined mechanism of aggregation induced emission (AIE)
and excited-state intramolecular proton transfer (ESIPT), which
can avoid ACQ effect and make the designed compound G an
excellent donor. Upon addition of WP6 to the aqueous solution
of G, it was found that the trimethylammonium terminals of G
could form stable inclusion complex with WP6 and further self-
assembled into spherical nanoparticles, which can not only
significantly lower the critical aggregation concentration of G but
also can remarkably improve the AIE effect of G. Hydrophobic
fluorescent dye NiR or ESY, which acts as an idea acceptor,
was successfully loaded within the hydrophobic interior of the
obtained nanoparticles. To our delight, efficient energy-transfer
process took place from the WP6-G assembly not only to NiR
but also to ESY for these two different systems. Furthermore,
both of the WP6-G-NiR and WP6-G-ESY systems show
ultrahigh antenna effect at a high donor/acceptor ratio.
solvent-dependent aggregation behavior. The emission of G (1 ×
10-4 M) was very weak in DMSO, and it increased slowly when
the water content was less than 80 vol%. However, when the
water content increased from 80 to 100 vol%, the fluorescence
intensity of G enhanced significantly caused by the intriguing
AIE effect due to the formation of aggregates at this
concentration.[12] And the aqueous solution of G (1 × 10-4 M)
showed strong yellow fluorescence under 365 nm excitation.
Based on the above-mentioned result, we wonder whether
WP6 could induce G to assemble into higher-order aggregates
and lead to remarkable emission enhancement of G in aqueous
solution. Interestingly, upon addition of WP6 to the aqueous G
solution, obvious Tyndall effect could be observed, indicating the
existence of plentiful nanoparticles (Figure S10b, Supporting
Information). Moreover, the fluorescence intensity of
G
increased significantly, and the fluorescence enhancement could
be clearly perceived by the naked eye (Figure S10d, Supporting
Information), which suggests that WP6 could induce G to
assemble into tightly stacked aggregates and resulted in the AIE
effect via restriction of intramolecular rotation of G around the
N–N bond.[12] In the control experiment, neither Tyndall effect
nor fluorescence enhancement could be observed, when the
building subunit of WP6 was added to the G solution (Figure
S11, Supporting Information), indicating that the macrocycle-
based host–guest recognition is crucial for inducing G to
assemble. Then, the critical aggregation concentration (CAC) of
G with WP6 for the formation of supramolecular aggregates was
measured by monitoring optical transmittance. The CAC of free
G was determined to be 1.4 × 10-4 M, and the transmittance of G
at 500 nm showed no discernible change when the
concentration of G is below its CAC (Figure S12, Supporting
Information). However, upon gradual addition of WP6 to the G
solution (2 × 10-5 M, below its CAC), the solution transmittance
at 500 nm underwent first decrease and then an inverse
increase, and an inflection point with the molar ratio 4:1
([G]/[WP6]) was observed when plotting the optical
transmittance at 500 nm versus WP6 concentration (Figure S13,
Supporting Information), which indicates that the best mixing
ratio of G and WP6 for the assembly was 4:1. Moreover,
keeping the mixing ratio of G and WP6 at their best molar ratio,
WP6 was synthesized according to reported method,[11] and G
was obtained by using 2,4-dihydroxybenzaldehyde as starting
material.
Since
G
shows
poor
water
solubility,
butyltrimethylaminium bromide (GM) was used as a model
compound to study the host–guest complexation between WP6
and G. As shown in Figure S7, upon adding equal equivalent of
WP6 to the solution of GM, the signals of phenyl protons (H1) and
methylene protons (H2 and H3) from WP6 shifted downfield
slightly. Whereas, the signals derived from N-methyl protons
(Ha) and butyl protons (Hb, Hc, Hd, and He) of GM shifted upfield
remarkably and showed obvious broadening effect due to the
shielding effect of the electron-rich cavities of pillar[6]arene. The
above observations demonstrated that the alkyl chain of GM was
encapsulated into the hydrophobic cavity of WP6. Moreover, a
1:1 binding stoichiometry between WP6 and GM for the
WP6⊃GM inclusion complex was measured by Job’s plot method
(Figure S8, Supporting Information), and the association
constant (Ka) between WP6 and GM was determined to be 2.31
×
102 M-1 by 1H NMR titration experiments (Figure S9,
Supporting Information).
the CAC for WP6-G assembly was determined to be 5 × 10-6
M
(Figure S14, Supporting Information), which means that the CAC
value of G decreased at least 28-fold in the presence of WP6.
Furthermore, the fluorescence changes of G with different
amounts of WP6 were monitored. As shown in Figure 2b, the
fluorescence of G (2 × 10-5 M) first increased upon addition of
WP6, reaching a maximum at a WP6 concentration of 5 × 10-6 M,
which is coincidental with the best molar ratio of G and WP6,
and then the fluorescence decreased upon further addition of
WP6. The increase in fluorescence indicated the formation of
aggregates by mixing G and WP6. Compared with free G, the
fluorescence intensity of G with the presence of WP6 increased
30 times at the maximum point, indicating that the AIE effect of
G was significantly improved by WP6 at the best mixing ratio.
Such a WP6-improved AIE effect of G was also in accoredance
with the sharp increase of fluorescence quatum yield of the
obtained WP6-G assembly (5.32%, Table S3, Supporting
Information).12 Whereas, further addition of excessive amount of
WP6 led to the formation of a simple 2:1 WP6⊃G inclusion
Figure 1. (a) Fluorescence spectra of G (1 × 10-4 M) in a DMSO/H2O mixed
solution with different vol% (λex = 365 nm); (b) Fluorescence intensity of G at
510 nm in the presence of different faction of water from 10 to 100%. Inset:
photographs of G (1 × 10-4 M) in DMSO/H2O = 9:1 (left) and in water (right)
under UV lamp irradiation.
The fluorescence of G was first studied in a DMSO/water
mixed solution with different water fractions to investigate its
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complex and accompanied by the disassembly of the
aggregates, resulting in an obvious decrease in the fluorescence
intensity.
salicylaldehyde azine groups tend to form π-π stacked
structure[13] and the complexation with WP6 could
counterbalance the original charge repulsion of G, then free G
and complexed G integrate together to form curved aggregate,
which further self-assemble to form a multilayer sphere with
alternating shell structure as illustrated in Scheme 1.[14]
Moreover, the ζ-potential experiment suggested that these
nanoparticles have a relatively high negative ζ-potential (–29.6
mV, Figure S16, Supporting Information), indicating the
existence of repulsive forces among these nanoparticles which
can enhance their stability.
As the WP6-G assembly showed remarkably enhanced
fluorescence in aqueous solution, it will be an idea candidate to
fabricate aqueous artificial light-harvesting systems, which could
avoid fluorescence self-quenching of the aggregated donor
chromophores in aqueous solution. Hydrophobic fluorescence
dye nile red (NiR) was first selected as a fluorescent acceptor,
since the absorption band of NiR is largely overlapped with the
fluorescence band of the WP6-G assembly (Figure S17,
Supporting Information). As show in Figure 4a, with the gradual
addition of NiR to the WP6-G assembly, the fluorescence
intensity of the WP6-G assembly decreased, while the
fluorescence emission of NiR (acceptor) increased when excited
at 365 nm. In contrast, the emission of free NiR was negligible
upon direct excitation at 365 nm or even at 580 nm (Figure S18,
Supporting Information). The quatum yield of WP6-G-NiR
assembly also showed a sharp increase (10.69%, Figure S20,
S21 and Table S3, S4, Supporting Information), probably
becacuse NiR accepts and emits the maximum possible amount
of excitation energy.6d Therefore, the above phenomenon
indicates that energy transfer takes place from the WP6-G
assembly to the encapsulated NiR. Moreover, fluorescence
decay experiments were performed to support the occurrence of
light-harvesting process. The decay curve of G (Figure 4b, blue
line) was fitted as a double exponential decay with fluorescence
lifetimes of τ1 = 0.32 ns and τ2 = 1.62 ns, both of which were
related to the tightly stacked G (Table S1 and S2, Supporting
Information). For the WP6-G assembly (Figure 4b, green line),
the fluorescence lifetimes increased to τ1 = 0.70 ns and τ2 = 1.95
ns due to WP6-induced aggregation of G. With respect to the
WP6-G-NiR assembly (Figure 4b, red line), the fluorescence
lifetimes decreased to τ1 = 0.61 ns and τ2 = 1.69 ns, which
further validates that energy transfer takes place from the WP6-
G donor to NiR acceptor (Table S1, Supporting Information).[3b]
These results also jointly suggested that NiR was encapsulated
within the WP6-G nanoparticles. Moreover, the morphology and
size distribution of NiR-loaded WP6-G assembly were similar to
that of WP6-G nanoparticles based on the DLS and TEM results
(Figure S15c and 15d, Supporting Information).
Figure 2. (a) Fluoresence spectra of G (2 × 10-5 M) upon increasing the
concentration of WP6 (0 － 2 × 10-5 M). (b) Dependence of fluorescence
intensity at 514 nm on the WP6 concentration (0 – 2 × 10-5 M) with a fixed
concentration of G (2 × 10-5 M). Inset: photographs of G (2 × 10-5 M) (left) and
the mixture of G (2 × 10-5 M) and WP6 (5 × 10-6 M) (right) under UV lamp
irradiation.
Subsequently, the morphology and size of the formed
aggregates were investigated by dynamic light scattering (DLS),
transmission electron microscopy (TEM), and scanning
electronic microscopy (SEM) measurements. DLS results
showed that the WP6-G complex (at the best mixing ratio)
formed well-defined aggregates with a narrow size distribution,
giving an average diameter of 109 nm (Figure 3a). The TEM and
SEM images showed spherical morphology with a dark core and
the diameters around 100 nm (Figure 3c), indicating that they
formed spherical nanoparticles. Confocal fluorescence images
further showed that these nano-aggregates exhibited strong
fluorescence (Figure 3b). The formation of WP6-G nanoparticles
might proceed as follows: Upon addition of WP6,
supramolecular inclusion complex was formed by WP6 and G
based on electrostatic and hydrophobic interactions. Since the
Furthermore, the energy transfer efficiency and antenna effect
which are widely used empirical parameters to evaluate the
efficiency of a light-harvesting system, were investigated for the
WP6-G-NiR assembly.[3c] The energy transfer efficiency, which
was estimated from the fluorescence quenching rate of G in the
aggregated structure, reached 55% when the mixing molar ratio
of donor/acceptor was at 150:1 (Figure S22, Supporting
Information). Notably, the antenna effect at this mixing ratio was
calculated to be 25.4 (Figure S23 Supporting Information), which
Figure 3. (a) DLS data of WP6-G assembly at 25 °C . (b) Fluorescence
microscopic image of the WP6-G aggregates. (c) TEM image of WP6-G
assembly. (d) SEM image of WP6-G assembly. ([WP6] = 5 × 10-6 M, [G] = 2 ×
10-5 M).
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indicates that the WP6-G nanoparticles function as an excellent
light harvesting antenna in aqueous environment.
S5, Supporting Information), confirming the energy transfer from
the WP6-G donor to ESY acceptor. These results also indicated
that ESY was loaded within the WP6-G nanoparticles. In
addition, the morphology and size distribution of WP6-G-ESY
assembly were also similar to that of the WP6-G assembly
(Figure S15e and S15f, Supporting Information). The energy
transfer efficiency was estimated to be 42% when the mixing
molar ratio of donor/acceptor was at 200:1 (Figure S27,
Supporting Information). And the antenna effect was calculated
to be 28.0 at such high donor/acceptor ratio (Figure S28,
Supporting Information), indicating the ESY-loaded nanoparticle
could also function as an excellent light harvesting antenna in
aqueous environment.
In conclusion, highly efficient artificial light-harvesting
systems were fabricated in aqueous environment based on a
facile supramolecular self-assembly strategy. The easily
obtained WP6-G supramolecular assembly showed significantly
enhanced fluorescence due to an enhanced AIE effect. After
simply mixing WP6-G assembly with hydrophobic fluorescence
dye NiR or ESY, two atrtifical light-harvesting systems were
successfully constructed based on the highly efficient FRET
process that takes place from the donor (WP6-G assembly) to
the acceptor (NiR or ESY). More importantly, both of these two
artificial light-harvesting systems showed very high antenna
effect (25.4 for WP6-G-NiR assembly and 28.0 for WP6-G-ESY
assembly) with high donor/acceptor ratio (up to 150:1 for WP6-
G-NiR system and 200:1 for WP6-G-ESY system), which are
similar to that of natural light-harvesting system. Therefore,
these highly efficient aqueous artificial light-harvesting systems
are very important and versatile platform for mimicking
photosynthesis.
Figure 4. (a) Fluorescence spectra of WP6-G ([WP6] = 5 × 10-6 M, [G] = 2 ×
10-5 M) in water with different concentrations of NiR. Inset: photographs of
WP6-G and WP6-G-NiR ([WP6] = 5 × 10-6 M, [G] = 2 × 10-5 M, [NiR] = 1.3 ×
10-7 M). (b) Fluorescence decay profiles of G (blue line), WP6-G (green line),
and WP6-G-NiR (red line). ([WP6] = 5 × 10-6 M, [G] = 2 × 10-5 M, [NiR] = 1.3 ×
10-7 M). (c) Fluorescence spectra of WP6-G ([WP6] = 5 × 10-6 M, [G] = 2 × 10-5
M) in water with different concentrations of ESY. Inset: photographs of WP6-G
and WP6-G-ESY ([WP6] = 5 × 10-6 M, [G] = 2 × 10-5 M, [ESY] = 1 × 10-7 M).
(d) Fluorescence decay profiles of G (blue line), WP6-G (green line), and
WP6-G-ESY (yellow line). ([WP6] = 5 × 10-6 M, [G] = 2 × 10-5 M, [ESY] = 1.0 ×
10-7 M).
Moreover, we also used hydrophobic eosin Y (ESY) as a
fluorescent acceptor to fabricate another light-harvesting system
with WP6-G assembly, since the absorption band of ESY is also
largely overlapped with the fluorescence band of the WP6-G
assembly (Figure S24, Supporting Information). Upon gradual
addition of ESY to the WP6-G assembly, the fluorescence
intensity of the WP6-G assembly decreased, whereas the
fluorescence emission of ESY increased when excited at 365
nm (Figure 4c). On the contrary, the emission of free ESY was
negligible upon direct excitation at 365 nm or even at 510 nm
(Figure S25, Supporting Information). The quatum yield of WP6-
G-ESY assembly also showed a sharp increase (10.69%, Figure
S20, S21 and Table S3, S4, Supporting Information), which is
probably also becacuse ESY accepts and emits the maximum
possible amount of excitation energy.6d Thus, the above
phenomenon clearly indicated the occurrence of energy transfer
between the WP6-G assembly and ESY. Subsequently, the
fluorescence decay measurements further validate the light-
harvesting process. Herein, to make sure that the fluorescence
mostly corresponds to the donor, the monitored wavelength was
selected at 500 nm, which is little lower than the donor emission
maxima (513 nm). Similar to the values of the WP6-G assembly
monitored at 513 nm, the assembly monitored at 500 nm (Figure
4d, green line) also showed fluorescence lifetimes of τ1 = 0.81
ns and τ2 = 1.99 ns (Table S5, Supporting Information). However,
the fluorescence lifetimes of the WP6-G-ESY assembly (Figure
4d, yellow line) decreased to τ1 = 0.44 ns and τ2 = 1.43 ns (Table
Acknowledgements
This work was supported by the National Basic Research
Program of China (2014CB846004) and the National Natural
Science Foundation of China (No. 21572101, 21472089). Xiao-
Yu Hu also thanks the Alexander von Humboldt Foundation for a
research fellowship.
Keywords: light harvesting • aggregation-induced emission •
pillar[6]arene • host-guest interaction • supramolecular self-
assembly
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This article is protected by copyright. All rights reserved.

10.1002/anie.201800175
Angewandte Chemie International Edition
COMMUNICATION
COMMUNICATION
Shuwen Guo, Yongshang Song, Yuling
He, Xiao-Yu Hu,* and Leyong Wang,*
Page No. – Page No.
Highly Efficient Artificial Light-
Harvesting Systems Constructed in
Aqueous Solution Based on
Supramolecular Self-Assembly
Highly efficient light-harvesting systems are successfully fabricated in aqueous solution based on the supramolecular self-assembly
of a water-soluble pillar[6]arene (WP6), a salicylaldehyde azine derivative (G), and two different fluorescence dyes, nile red (NiR) or
eosin Y (ESY). The WP6-G supramolecular assembly exhibits remarkably improved aggregation-induced emission enhancement and
acts as a donor for the artificial light-harvesting system, and NiR (or ESY) which is loaded within the WP6-G assembly acts as
different acceptors. Notably, efficient energy-transfer process takes place from the WP6-G assembly not only to NiR but also to ESY
for these two different systems. Furthermore, both of the WP6-G-NiR and WP6-G-ESY systems show ultrahigh antenna effect at a
high donor/acceptor ratio.
This article is protected by copyright. All rights reserved.