Acetal-based spirocyclic skeleton bridged tetraphenylethylene dimer for light-harvesting in water with ultrahigh antenna effect

Article abstract of DOI:10.1016/j.dyepig.2021.109161

Herein an aqueous-phase artificial light-harvesting platform has been constructed based on the self-assembly of three small organic molecules: a rigid acetal-based spirocyclic skeleton bridged tetraphenylethylene dimer as donor, a hydrophobic dye molecule

Full text of DOI:10.1016/j.dyepig.2021.109161

Dyes and Pigments 188 (2021) 109161
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Dyes and Pigments
journal homepage: http://www.elsevier.com/locate/dyepig
Acetal-based spirocyclic skeleton bridged tetraphenylethylene dimer for
light-harvesting in water with ultrahigh antenna effect
*
**
Tangxin Xiao , Xiaoyan Wei, Haoran Wu, Kai Diao, Zheng-Yi Li, Xiao-Qiang Sun
School of Petrochemical Engineering, Changzhou University, Changzhou, 213164, China
A R T I C L E I N F O
A B S T R A C T
Keywords:
Herein an aqueous-phase artificial light-harvesting platform has been constructed based on the self-assembly of
three small organic molecules: a rigid acetal-based spirocyclic skeleton bridged tetraphenylethylene dimer as
donor, a hydrophobic dye molecule Nile Red as acceptor, and the surfactant cetyltrimethyl ammonium bromide
as amphiphile to enwrap the donor and acceptor and disperse them in water. Due to the rigid skeleton of the
tetraphenylethylene dimer that can well accommodate and distribute Nile Red inside the self-assembled nano-
spheres, the system shows ultrahigh light-harvesting antenna effects. Moreover, by simply tuning the donor/
acceptor molar ratio, tunable emission including a bright white-light emission could be realized.
Light-harvesting
Self-assembly
Nanoparticles
TPE
Spirocyclic skeleton
1
. Introduction
34], fluorescent sensors [35,36], and organic luminescent materials [37,
3
8]. The antenna effect (AE) [39,40], an empirical value for measuring
Light-harvesting and energy transfer are extremely important pro-
light capture ability, of these systems reported in the past is usually
below 40 within a solution system. Therefore, exploiting new type of
scaffolds to further improve the light-capturing ability of the artificial
platform is highly desirable and remains a big challenge.
cesses in photosynthesis, which is the foundation for life to gain solar
energy [1–4]. The light-harvesting units are complex supramolecular
systems which organize a large number of chromophores like chloro-
phylls and carotenoids to collect light and transfer the energy to an
acceptor in reaction center [5–10]. Notably, the chromophores are fixed
inside rigid protein scaffolds with densely packed alignments, which
largely enhances the photon capture efficiency even in low light envi-
ronments [11–13]. Therefore, an efficient light-harvesting and energy
transfer process requires: firstly, a large number of antenna chromo-
phores (donor) with a specific alignment and which need to be located in
a confined space but can avoid aggregation-caused quenching (ACQ);
secondly, a rigid skeleton is more advantageous to align acceptor
chromophores, which can promote effective interchromophoric inter-
action [11], for example, the so-called F o¨ rster resonance energy transfer
Generally, rigid molecules with contorted structures, which can
prevent the molecule from densely packing in a confined space, are
necessary to create a high free volume inside the nanoparticles (NPs).
Therefore, some rigid molecules, which might contain non-planar mo-
lecular conformations, are used as a donor (D) scaffold [41]. The
spiro-centered and rotation-hindered structure is often employed for
microporous organic polymers [42,43], for example, acetal-based spi-
rocyclic skeleton synthesized from pentaerythritol and aromatic acetyl
derivatives. Inspired by this, we have prepared a Zn(II) fluorescent
probe by using such spirocyclic skeleton bridged Schiff base dimer [44].
Based on our previous works on supramolecular self-assembly [45–49]
and a recent work on supramolecular polymer-based light-harvesting
(
FRET) process [14]. To meet the first requirement, aggregation-induced
emission (AIE) molecules reported by Tang and co-workers shed a
shining light on this research area [15,16]. For the second requirement,
various artificial light-harvesting scaffolds have been constructed in
recent years, such as porphyrin arrays [5,17–19], supramolecular co-
ordination complexes [20–22], hydrogels [23,24], hybrid assemblies [7,
system
[50],
we
envisioned
that
the
combination
of
pentaerythritol-based acetal spirocyclic skeleton with AIE group would
be a useful idea to create a more efficient and concise light-harvesting
system. Hence, we designed and synthesized such a simple molecule
DTPE, an acetal-based spirocyclic skeleton bridged tetraphenylethylene
(TPE) dimer, to serve as antenna donors (Fig. 1). By employing a
so-called mini-emulsion strategy [51,52], supramolecular NPs based on
2
5], conjugated polymers [26], and self-assembled nanoparticles
[
27–32]. These artificial systems are usually used for bioimaging [28,33,
*
Corresponding author.
* Corresponding author.
E-mail addresses: xiaotangxin@cczu.edu.cn (T. Xiao), xqsun@cczu.edu.cn (X.-Q. Sun).
*
https://doi.org/10.1016/j.dyepig.2021.109161
Received 4 November 2020; Received in revised form 14 January 2021; Accepted 14 January 2021
Available online 18 January 2021
0
143-7208/© 2021 Elsevier Ltd. All rights reserved.

T. Xiao et al.
Dyes and Pigments 188 (2021) 109161
Fig. 1. Schematic illustration of the self-assembly of an artificial light-harvesting system based on DTPE and Nile Red.
DTPE in water can be constructed with the assistance of cetyltrimethyl
ammonium bromide (CTAB). Notably, the hydrophilic head of CTAB
located on the outer surface of the NPs plays the role not only for
dispersing the organic molecules in water, but also mimicking the
membrane in real photosynthetic system. Upon loading a hydrophobic
dye Nile Red (NR) as an acceptor (A), an efficient energy transfer system
in water was achieved with an ultrahigh antenna effect (AE = 66), which
is much larger than recent reports on artificial light-harvesting system in
solution [26,27]. Moreover, the emission of the NPs can be tuned by
simply adjusting D/A ratio, which includes an accurate white-light
emission. As a result, the DTPE/NR system appeared to be a novel
and outstanding light-harvesting system with potential applications in
luminescent materials.
2
. Experimental section
2
.1. Materials and methods
Scheme 1. Synthesis of DTPE.
Unless otherwise noted, all chemical reagents and solvents were
commercially available and were used without further purification. If
needed, solvents were dried by literature known procedures. All yields
were given as isolated yields. The 1H NMR and C NMR spectra were
recorded with a Bruker AVANCE III (300 MHz) spectrometer and cali-
brated against the residual proton signal or natural abundance carbon
resonance of the used deuterated solvent from tetramethylsilane (TMS)
as the internal standard. The chemical shifts δ are indicated in ppm and
the coupling constants J in Hz. The multiplicities are given as s (singlet),
d (doublet), dd (doublet of doublets), t (triplet), and m (multiplet). High-
resolution electrospray ionization mass spectra (HR-ESI-MS) were
recorded on an Agilent Technologies 6540 UHD Accurate-Mass. SEM
investigations were carried out on a JSM-6360LA instrument. TEM
investigations were carried out on a JEM-2100 instrument. DLS mea-
surements were carried out on a Brookhaven BI-9000AT system,
equipped with a 200 mW polarized laser source (λ = 514 nm) at a
13
◦
scattering angle of 90 . All samples were prepared according to the
corresponding procedures mentioned above. The UV–Vis absorption
spectra were measured on a PerkinElmer Lambda 35 UV–Vis Spec-
trometer. Fluorescence measurements were performed on an Agilent
Cary Eclipse spectrofluorometer. The fluorescence lifetimes were
measured employing time correlated single photon counting on a FS5
instrument with a pulsed xenon lamp. Analysis of fluorescence decay
curves were subjected to fit a bi-exponential decay. The instrument
response function (IRF) measures the scattering of laser excitation from
2

T. Xiao et al.
Dyes and Pigments 188 (2021) 109161
water was added dropwise to the mixture. The mixture was stirred at
room temperature for 30 min. Tetrakis (triphenylphosphine) palladium
(
0.23 g, 0.2 mmol) was added quickly and the reaction mixture was
◦
heated to reflux at 90 C for 24 h. After cooling to room temperature, the
reaction mixture was diluted with water and extracted with ethyl ace-
tate (50 mL × 3). The organic layer was combined and dried with
4
anhydrous MgSO . The crude product was purified by silica gel chro-
matography (PE: EA = 3 : 1, v/v) to afford compound 1 as a yellow solid
1.35 g, 93%). Mp. 156–157 C [54]; 1H NMR (300 MHz, CDCl
◦
) δ
(
(
3
ppm): 9.90 (s, 1H, CHO), 7.63–7.60 (m, 2H, ArH), 7.20–7.18 (m, 2H,
ArH), 7.14–7.11 (m, 9H, ArH), 7.03–7.01 (m, 6H, ArH) (Fig. S7).
2
.2.2. Synthesis of DTPE
To a flask equipped with a magnetic stirrer, compound 1 (1.89 g, 5.2
mmol), p-toluenesulfonic acid (0.03 g, 0.1 mmol), and toluene (50 mL)
were charged under an argon atmosphere. A suspension of pentaery-
thritol (0.35 g, 2.6 mmol) in toluene (50 mL) was added to the mixture.
The reaction mixture was heated to reflux for 6 h. After cooled down to
room temperature, the reaction mixture was extracted with DCM (50
mL × 3). The organic layer was dried with anhydrous MgSO
4
. The crude
product was purified by silica gel chromatography (PE: EA = 2 : 1, v/v)
to afford compound DTPE as a white solid (0.82 g, 38%). Mp.
◦
1
1
49.6–151.3 C; H NMR (300 MHz, CDCl
H, ArH), 7.10–6.96 (m, 34H, ArH), 5.35 (s, 2H, CH), 4.80 (d, J = 10.8
), 3.78 (d, J = 11.6 Hz, 4H, CH ), 3.59 (d, J = 11.6 Hz, 2H,
) (Fig. S8); 13C NMR (75 MHz, CDCl
) δ (ppm): 144.7, 143.7, 143.6,
3
) δ (ppm): 7.21 (d, J = 8.2 Hz,
4
Hz, 2H, CH
CH
2
2
2
3
1
1
43.5, 141.3, 140.4, 135.8, 131.4, 131.3, 127.8, 127.6, 126.5, 126.4,
25.5, 102.4, 71.1, 70.6, 32.5 (Fig. S9); HRMS (ESI): m/z calcd. for
+
C
59
H
49
O
4
821.3625 [M + H] , found: 821.3606 (Fig. S10).
2
.3. Preparation of the NPs
Different types of DTPE/NR in a certain molar ratio (80:1, 100:1,
1
50:1, 200:1, 250:1, 500:1, 750:1, and 1000:1) were dissolved in a small
amount of chloroform (250 L) with a constant DTPE concentration (2
μ
2 2
Fig. 2. (a) Fluorescence spectra of DTPE versus H O fraction in THF/H O
mM). This organic solution was emulsified in water (10 mL) by ultra-
sonication with CTAB as a surfactant (0.8 mM). By centrifuging and
decanting the supernatant, the obtained NPs could be observed by SEM.
mixtures. Inset: photographs of DTPE in pure THF (left) and mixed solvent with
5% H O (right). (b) Fluorescence spectra of molecule DTPE in CHCl and NPs
of DTPE in water. Inset: the Tyndall effect of (1) DTPE in CHCl and (2) NPs of
and (4) NPs of DTPE in water
9
2
3
3
DTPE in water; photographs of (3) DTPE in CHCl
3
under UV lamp irradiation. λex = 365 nm, [DTPE] = 5 × 10ꢀ M.
5
3. Results and discussion
3
.1. AIE property and preparation of NPs
non-fluorescent control samples to determine the fastest possible
response of the detectors. The quantum yields were carried out on a FS5
instrument with the integrating sphere. The CIE (Commission Inter-
nationale de l’Eclairage) 1931 coordinates were calculated with the
method of color matching functions.
To ensure the AIE property of DTPE, the emission of DTPE in THF/
2
H O solutions were tested. As shown in Fig. 2a, there is no emission
when it was dissolved in pure THF (a good solvent). When the water (a
poor solvent) content was gradually increased to 65%, a moderate
2
emission was observed. As H O increased to 90%, the fluorescence in-
2
.2. Synthesis
tensity shows a prominent continuous increase. This excellent AIE
property encourages us to prepare fluorescent NPs based on DTPE,
which were prepared by the mini-emulsion method [51,52]. To an
aqueous solution of CTAB (10 mL, [CTAB] = 0.8 mM), DTPE (2 mM) in
As shown in Scheme 1, compound DTPE was synthesized by Suzuki
coupling reaction of bromotriphenylethylene and 4-formylphenylbor-
onic acid followed by acetalization of the resulting intermediate 1
with pentaerythritol under nitrogen protection.
CHCl
3
(250 L) was added, followed by ultrasonication for 30 min to
μ
afford the NPs. The formation of luminescent NPs was first evidenced by
the Tyndall effect and AIE phenomenon. The aqueous solution of DTPE
dispersed by CTAB shows a clear Tyndall effect, indicating the formation
of nanoaggregates (Fig. 2b, inset: (2)). By contrast, the solution of DTPE
2
.2.1. Synthesis of 1
Compound 1 was synthesized according to literature report [53]. To
a flask equipped with a magnetic stirrer, bromotriphenylethylene (1.34
g, 4.0 mmol), 4-formylphenylboronic acid (0.90 g, 6.0 mmol), and THF
in CHCl
CHCl (Fig. 2b, inset: (1)). Furthermore, the NPs exhibited strong blue
fluorescence due to AIE under UV lamp irradiation (Fig. 2b, inset: (4)).
On the contrary, the solution of DTPE in CHCl has no fluorescence
3
has no Tyndall effect owing to its molecular dissolution in
3
(
40 mL) were charged under a nitrogen atmosphere. A solution of tet-
rabutylammonium bromide (0.01 g) and K CO (0.66 g, 4.8 mmol) in
2
3
3
3

T. Xiao et al.
Dyes and Pigments 188 (2021) 109161
Fig. 3. (a) Normalized emission spectra of DTPE NPs in water and NR in CHCl
3
, respectively (λex = 365 nm), and normalized absorption spectrum of both DTPE and
◦
NR in water. (b) DLS data of DTPE/NR NPs in water at 25 C. (c) SEM image of DTPE/NR NPs. (d) TEM image of DTPE/NR NPs. Composition of the NPs: CTAB
micelles including DTPE and NR, molar ratio of DTPE/NR = 80/1 ([DTPE] = 5 × 10ꢀ 5 M).
under the same condition (Fig. 2b, inset: (3)). These phenomena can also
be observed from fluorescence spectra (Fig. 2b). The absolute fluores-
cence quantum yield of the resultant NPs was determined to be 36.72%
by employing an FS5 fluorescence spectrometer (Edinburgh Instrument)
suggested that the NPs are well-defined nano-assemblies with a narrow
distribution, presenting an average hydro-dynamic diameter of 174 nm
(Fig. 3b). The SEM and TEM images of the NPs showed a regular
spherical morphology with diameters around 150 nm (Fig. 3c and d).
(
Fig. S3a). The remarkable emission of DTPE NPs in water should be due
to the restriction of motion of TPE group in a confined space.
3
.3. The energy transfer process and antenna effect of DTPE/NR NPs
With the DTPE/NR NPs in hand, the energy transfer process and
3
.2. Absorption and emission spectra and morphologies of DTPE/NR NPs
antenna effect were thoroughly studied. Titration of NR gradually
lowered the emission of DTPE (donor, D) at 471 nm while enhanced that
of the NR (acceptor, A) at 583 nm when excited at 365 nm (Fig. 4a).
Meantime, the fluorescent color was changed from blue to red (Fig. 4a,
inset). These observations clearly indicate that energy transfer has
occurred from the donor to the acceptor. Simultaneously, the fluores-
cence quantum yield of DTPE/NR NPs (37.67%; Fig. S3b) shows a
similar value to individual DTPE NPs, suggesting that the ternary NPs
maintained a good fluorescence stability in water. To evaluate the en-
Considering the excellent AIE property and the potential nano-
channels inside the NPs due to the rigid acetal-based spirocyclic skel-
eton of DTPE, the NPs would be an ideal candidate for fabricating
artificial light-harvesting platform. Therefore, the commercially avail-
able dye NR was selected as an energy acceptor owing to the good
overlap between emission spectrum of the DTPE and absorption spec-
trum of NR (Fig. 3a). It should be noting that the absorption spectrum of
NR in Fig. 3a was normalized. The actual absorption intensity of the
acceptor (NR) at the donor excitation wavelength (365 nm) was negli-
gible, especially at low acceptor concentrations (a maximum of 1.25 mol
ergy transfer process more deeply, the energy-transfer efficiency (ΦET
)
of this system is measured. The calculation of ΦET is based on the fluo-
rescence quenching rate of DTPE. With D/A ratios of 80:1, 100:1, 150:1,
%
was used, D/A = 80/1), which ruled out the possibility for direct
200:1, 250:1, 500:1, 750:1, and 1000:1, the ΦET resulted in 75.9%,
71.0%, 62.5%, 56.6%, 46.9%, 36.4%, 27.8%, and 15.3%, respectively
excitation of NR on excitation of the donor (Fig. S1). Thus, it is more
negligible when the quantity of NR is further reduced (D/A = 100/
(
Fig. S4 and Table S3).
1
–1000/1). Moreover, there is no emission when individual NR NPs in
In addition to evaluating the energy transfer process by employing
water was excited at 365 nm. Due to the potential nano-channels inside
the NPs, the hydrophobic NR can be easily loaded into the hydrophobic
micro-environment of the NPs by mini-emulsifying DTPE and NR
simultaneously. In this case, the distance between the donor and the
acceptor will be greatly shortened, which guarantees an efficient FRET
process. The size and morphologies of DTPE/NR NPs were characterized
by dynamic light scattering (DLS), scanning electron microscopy (SEM),
and transmission electron microscopy (TEM). DLS measurements
Φ
ET, the light-harvesting ability is evaluated by the “antenna effect
(
AE)”, the definition of which is the ratio of the fluorescence intensity of
the acceptor upon excitation of the donor to that of the direct excitation
of the acceptor [39]. In our case, the AE was calculated based on the
fluorescence enhancement ratio of NR:
AE = (IDA
,
365ꢀ ID,365)/IDA,471
(eq. 1)
4

T. Xiao et al.
Dyes and Pigments 188 (2021) 109161
aggregation-caused quenching therefore occurs. Thus, the acetal-based
spirocyclic skeleton is a key factor for the realization of efficient
light-harvesting capability.
In order to further investigate the energy transfer behavior inside the
NPs, time-resolved fluorescence experiments were carried out. The
transient fluorescence profiles were fitted by a double exponential
decay. The NPs with individual DTPE showed the fluorescence lifetimes
of
τ
1
= 3.29 ns and
τ = 7.52 ns when detecting at 471 nm (Fig. 4b and
2
Table S1). On the contrary, the fluorescence lifetimes of the DTPE/NR
NPs (D/A = 80/1) decreased to
τ
1
= 1.62 ns and
τ = 3.62 ns, demon-
2
strating that the energy was successfully transferred from DTPE donor to
the NR acceptor, which is consistent with steady-state fluorescence
spectroscopy. These data suggest that the resultant DTPE/NR NPs can
act as an ideal light-harvesting platform in aqueous solution.
3
.4. The tunable emission property of DTPE/NR NPs
Thanks to the flexibility of the construction strategy, the tunable
emission property of the DTPE/NR NPs was further investigated. As we
can see from the CIE 1931 chromaticity diagram (Fig. 5a), the systems
exhibited D/A ratio-dependent fluorescence variations. The NPs with
individual DTPE locates in the blue area. With the D/A ratio decreased
from 1000:1 to 80:1, the fluorescence color changed from blue to red
gradually (Fig. 5a and c) due to the different extent of the energy
transfer. It is noteworthy that a white-light emission was achieved when
the molar ratio of D/A = 150:1 (Fig. 5a and c). The white-light fluo-
rescence color was tested to be (0.33, 0.32) in the CIE coordinate
(
Fig. 5a), which is in line with the pure white color coordinate (0.33,
0.33). At this moment, the ΦET is 62.5% and the antenna effect is up to
55. Moreover, the white fluorescence quantum yield is 42.63%, which
was continuously enhanced with the increasing acceptor (Fig. S3c). The
fluorescence lifetimes of the white-light NPs were determined to be
.62 ns and
= 5.72 ns, which were shorter than individual DTPE but
1
τ =
2
τ
2
longer than NPs with D/A = 80:1. This artificial light-harvesting system
is not only stable in solution but also stable in the solid-state, which is
evidenced by the application of such system for security ink. Upon
writing the pre-prepared solutions on an art paper, no colorful letter was
observed under natural light (Fig. 5b, upper), but obvious colorful letters
including a white letter “W” were clearly observed under a UV lamp
irradiation (Fig. 5b, down). Compared to conventional fluorescent inks,
the resultant fluorescent ink is an aqueous system with AIE property. It
can emit bright fluorescence both in aqueous solution and in the solid
state (eg. words on paper). Furthermore, the color (emission) of such
fluorescent ink could be continuously tuned from blue through white to
red just by simply adjusting the D/A ratio. As a result, we successfully
use this energy transfer system to achieve data encryption and anti-
counterfeiting functions.
Fig. 4. (a) Fluorescence spectra of DTPE/NR NPs in water with different
ꢀ 5
concentrations of NR. Inset: photographs of NPs of DTPE ([DTPE] = 5 × 10
ꢀ
5
ꢀ 7
M) and DTPE/NR ([DTPE] = 5 × 10 M, [NR] = 6.25 × 10 M). (b) Fluo-
ꢀ 5
rescence decay profiles of NPs of DTPE and DTPE/NR. [DTPE] = 5 × 10 M,
7
[
NR] = 6.25 × 10ꢀ M.
Where IDA,365 and IDA,471 are the fluorescence intensities of NR at
5
83 nm upon excitation of the NPs at 365 nm (excitation of the donor)
and at 471 nm (the direct excitation of NR), respectively. ID,365 is the
residual fluorescence intensity of the individual DTPE NPs at 583 nm
when excited at 365 nm, which was normalized with the DTPE-NR as-
sembly at 471 nm. Due to the fluorescence intensity of NR at 583 nm
includes the residue of DTPE, the actual fluorescence intensity of NR at
5
83 nm should be adjusted by subtracting ID,365.
With increasing D/A ratios from 80:1 to 100:1, 150:1, 200:1, 250:1,
00:1, 750:1, and 1000:1, the AE were calculated to be 46, 51, 55, 62,
6, 58, 48, and 44, respectively (Fig. S5 and Table S4). It is worth noting
5
6
4. Conclusions
that the AE can reach 66 when D/A is 250:1 (ΦET = 46.9%). To the best
of our knowledge, this is the highest AE in an aqueous system compared
to previous reports [26,27]. In a control experiment, by employing a
monomer compound tetraphenylethylene (TPE), which is without the
rigid spirocyclic structure, as donor to construct NPs (Scheme S1), the
fluorescence intensity of TPE decreased upon the addition of NR
In conclusion, a highly efficient light-harvesting system in water has
been self-assembled by employing three small organic molecules: CTAB
as surfactant, DTPE as donor, and NR as acceptor. Owing to the special
rigid spirocyclic structure of the donor, the acceptor could be distributed
rationally inside the NPs to avoid ACQ and induce efficient FRET pro-
cess. By simply adjusting the D/A ratio, tunable emission including a
white-light emission can be realized. Notably, an ultrahigh antenna ef-
fect of 66 was achieved at a higher donor/acceptor ratio of 250/1.
Moreover, such NPs are also stable in the solid state, endowing it with
the capability as security inks for anti-counterfeiting techniques. The
(
Fig. S6), suggesting that the energy could be absorbed by NR. However,
there is no emission peak from NR, indicating that the AE is 0. It may be
because NR cannot be well distributed in such NPs and
5

T. Xiao et al.
Dyes and Pigments 188 (2021) 109161
Fig. 5. (a) The CIE chromaticity diagram of photoluminescence color changes by varying the ratios of chromophores, and the white-light emitting coordinate. (b)
Letters written by the fluorescent inks: photographs under natural light (upper) and UV light (down). (c) Photographs of NPs in water with different D/A ratios.
current system opens a new window for mimicking light-harvesting and
developing new dynamic luminescent materials by employing the self-
assembly of simple organic molecules.
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