A General Strategy to Enhance the Performance of Dye-Sensitized Solar Cells by Incorporating a Light-Harvesting Dye with a Hydrophobic Polydiacetylene Electrolyte-Blocking Layer

Article abstract of DOI:10.1002/asia.201601722

A unique strategy to suppress charge recombination effectively and enhance light harvesting in dye-sensitized solar cells (DSSCs) is demonstrated by the design of a new dipolar organic dye functionalized with a diacetylene unit, which is capable of underg

Full text of DOI:10.1002/asia.201601722

CHEMISTRY
AN ASIAN JOURNAL
www.chemasianj.org
Accepted Article
Title: A general strategy to enhance the performance of dye-sensitized
solar cells by incorporating light-harvesting dye with hydrophobic
polydiacetylene electrolyte-blocking layer
Authors: Shih-Sheng Sun, Mekonnen Abebayehu Desta, and Chia-Wei
Liao
This manuscript has been accepted after peer review and appears as an
Accepted Article online prior to editing, proofing, and formal publication
of the final Version of Record (VoR). This work is currently citable by
using the Digital Object Identifier (DOI) given below. The VoR will be
published online in Early View as soon as possible and may be different
to this Accepted Article as a result of editing. Readers should obtain
the VoR from the journal website shown below when it is published
to ensure accuracy of information. The authors are responsible for the
content of this Accepted Article.
To be cited as: Chem. Asian J. 10.1002/asia.201601722
Link to VoR: http://dx.doi.org/10.1002/asia.201601722
A Journal of
A sister journal of Angewandte Chemie
and Chemistry – A European Journal

10.1002/asia.201601722
Chemistry - An Asian Journal
FULL PAPER
A General Strategy to Enhance the Performance of Dye-sensitized
Solar Cells by Incorporating Light-harvesting Dye with
Hydrophobic Polydiacetylene Electrolyte-blocking Layer
Mekonnen Abebayehu Desta,[a,b,c] Chia-Wei Liao[a] and Shih-Sheng Sun *[a]
Abstract: A unique strategy for effectively suppressing charge
recombination and enhancing light harvesting in dye-sensitized solar
cells (DSSCs) is demonstrated by designing a new dipolar organic
dye functionalized with a diacetylene unit, which is capable of
approaching of the oxidized redox mediator and supress the dark
current but also light-harvesting role by efficient energy transfer to
the dipolar dyes. A 15% efficiency improvement is achieved from
monomer dye (JSC = 13.5 mA/cm2, Voc = 0.728 V, FF = 0.73, η =
7.17%) to cross-linked dye (JSC = 14.9, Voc = 0.750, FF = 0.74, η =
undergoing photoinduced cross-linking reaction to generate
a
hydrophobic polydiacetylene layer. The polydiacetylene layer serves
as not only an electrolyte-blocking layer to effectively block the
8.27%) under AM1.5 condition.
with co-adsorbents, co-sensitization, and structurally engineered
sensitizers; most commonly by introducing of long alkyl
chains.[11]
Introduction
In the past two and half decades, dye-sensitized solar cells
(DSSCs) have received unprecedented attention both in industry
and academic research due to their cost effective manufacturing
processes and high photon-to-electron conversion efficiencies.[1]
A prototype DSSC consists of three components that play key
roles toward high power conversion ability; a photosensitizer
adsorbed on a nanocrystalline TiO2 film as the photoanode, a
counter electrode and redox electrolytes. Among them, the
sensitizers certainly play an important role as they are in charge
of light harvesting. Currently, the cell efficiencies (AM 1.5) of
single dye-based DSSCs have achieved 11% and higher.[2-4] To
further improve the performance of DSSCs in satisfying energy
demand, remarkable research efforts focusing on realizing the
complex TiO2/dye/electrolyte interfacial processes of DSSCs
have been devoted by designing novel sensitizers, electrolytes
combination and other new materials.[5] The power conversion
efficiency up to 14% has been achieved with collaborative
sensitization.[6]
Recently, a polystyryl-based organic sensitizer devised to
reduce the charge recombination has been reported.[12] However,
such modification is effective when the dye is cocktailed with the
co-adsorbent CDCA. Structural tuning on the hydrophobic side
chains of such system to limit the use of co-adsorbent and
optimization for satisfactory efficiency could be quite challenging.
In this work, therefore, we report a unique structural
modification by introducing the polydiacetylene (PDA) unit,
which in principle could be applied to any sensitizer to achieve
high cell efficiency without changing the current working
condition. The multiple applications of PDA system from the
development of organic films to immobilization of molecules[13]
inspired us to design a novel dipolar organic dye functionalized
with diacetylene unit in the peripheral position of the donor
moiety, where it can potentially undergo photopolymerization
under UV irradiation to form PDA blocking layer. The resulting
cross-linked hydrophobic layer in the exterior dye ensemble
would form a shield that effectively blocks the approaching of the
oxidized redox mediator and reduces the dark current. Moreover,
the conjugated network of PDA provides an additional light-
harvesting function that can enhance the photocurrent
generation by efficient energy transfer to the dipolar dyes.
One of the critical factors for an efficient DSSC is to slow
down the charge recombination process between the electrons
in the conduction band of TiO2 with the oxidized redox mediator
to suppress the dark current under working condition.[7] Thus,
searching for a better way to block charge recombination is
essential to the performance of DSSC and is urgently
demanding. Several strategies for minimizing such efficiency
loss in DSSCs have been reported including the coating of
inorganic barrier layers,[8] saccharides,[9] dendrimers,[10] cocktail
Results and Discussion
Synthesis
The synthetic routes for preparing the monomer, MA164, and
the model compound (12) are depicted in Scheme 1. The
synthesis began with commercially available 4-iodotoluene (1).
[a]
[b]
[c]
Mekonnen Abebayehu Desta, Chia-Wei Liao, Prof. Shih-Sheng Sun
Institute of Chemistry
Academia Sinica, Taipei, 115, Taiwan, Republic of China
E-mail: sssun@chem.sinica.edu.tw
Mekonnen Abebayehu Desta
1-(bromomethyl)-4-iodobenzene
iodophenyl)but-1-yn-1-yl)trimethylsilane (3)[15] were synthesized
with slight modification of the reference procedures.
(2)[14]
and
(4-(4-
a
Department of Chemistry,
National Tsing Hua University
Compound 9 was synthesized through a series of palladium(II)
catalyzed Buchwalde-Hartwig amination, Suzuki-Miyaura
borylation, Suzuki-Miyaura coupling reaction with 5,8-dibromo-
Hsinchu, 30013, Taiwan, Republic of China
Mekonnen Abebayehu Desta
Molecular Science and Technology,
Taiwan International Graduate Program (TIGP)
Taipei, 10617, Taiwan, Republic of China
2,3-diphenylquinoxaline,
and
desilylatation
and
in-situ
bromination, and Cadiot-Chodkiewicz coupling
methylpent-1-yne.
with 4-
† Electronic Supplementary Information (ESI) for this article can be found
under http://dx.doi.org/10.1002/asia.201601722.
For internal use, please do not delete. Submitted_Manuscript
This article is protected by copyright. All rights reserved.

10.1002/asia.201601722
Chemistry - An Asian Journal
FULL PAPER
i) CuCl, NH2OH.HCl,
30% pr-NH2 in H2O
N
N
ii) 4-methylpent-1-yne,
CH2Cl2, dark, rt.,
11
Si
12
Br
AgNO3, NBS,
dry acetone, dark, rt.,
Si
Si
Si
I
I
Si
NBS, CHCl3
dark, rt.,
Pd(OAc)2, [(CH3)3C]OK
benzoylperoxide
O
O
Pd(dppf)Cl2, KOAc
N
N
Br
N
B
n-BuLi,THF,
N2, -78 °C
[(CH3)3C]3P, toluene, 90 °C
NBS, CCl4, N2
reflux
dioxane, N2, 80 °C
6
2
1
3
5
I
4
Br
Br
Br
N
N
Pd(PPh3)2Cl2, Na2CO3
THF/H2O (2:1), N2, 50 °C
Br
N
N
N
N
O
Si
OH
OH
S
i) CuCl, NH2OH.HCl,
30% pr-NH2 in H2O
B
N
N
N
N
N
CNCH2COOH
AgNO3, NBS,
N
MA164
NH4OAC, AcOH
dark, 80 °C
dry acetone,
dark, rt.,
Pd(PPh3)2Cl2,
Na2CO3, N2
N
8
ii) 4-methylpent-1-yne,
CH2Cl2, dark, rt.,
N
Br
Br
S
Br
9
10
THF/H2O (2:1), 50 °C
7
O
Scheme 1. Synthesis of diacetylene-based organic dye (MA164) and the model compound 12
Knoevenagel condensation with cyanoacetic acid in the
presence of ammonium acetate yielded the target sensitizer
MA164. All the intermediates and final compounds were fully
characterized by using 1H and 13C NMR spectroscopy as well as
high-resolution mass spectrometry (HRMS). The data were all
consistent with the proposed molecular structures.
N
N
R
N
N
R
N
Optical and electrochemical properties
N
N
UV, 313 nm
R
N
Figure 1 illustrates the molecular structures and portion of the
cross-linked assemblies of the sensitizers. It is known that the
diacetylene derivatives undergo photo-polymerization in solution
through UV irradiation to produce a conjugated PDA network
with only minimal structural rearrangements.[16] The resulting
conjugated PDA networks often absorb light in the visible
spectral region.[17] Figure 2 shows the UV-vis absorption spectra
of MA164 recorded in DMF and the cross-linked sensitizer,
R
N
S
N
N
N
O
OH
N
N
S
MA164
MA164 AP
S
N
O
OH
MA164 AP, after
1 hour UV irradiation of MA164. The
N
O
corresponding data are summarized in Table 1. Two distinct
bands from 400 to 600 nm were observed for both dyes. The
band located at shorter wavelength is attributed to the π−π*
transition and the other at longer wavelength is attributed to the
internal charge transfer transition. Notable molar extinction
coefficient enhancement of the absorption between 375 to 500
nm was observed upon formation of the cross-linked D-A-π-A
structure owing to the extended π conjugation in PDA moiety. A
similar absorption enhancement in the visible region was
N
N
N
N
OH
N
R =
S
N
S
O
O
CR147
N
HO
HO
Figure 1. Molecular structures of the diacetylene monomer MA164, portion of
cross-linked assemblies MA164 AP, and the reference dye CR147
Subsequently, Suzuki-Miyaura coupling reaction of compound 9
with (5-formylthiophen-2-yl)boronic acid followed by
observed for
a model compound (12) with diacetylene
a
functionalized TPA-donor after photopolymerization (Figure S1).
For internal use, please do not delete. Submitted_Manuscript
This article is protected by copyright. All rights reserved.

10.1002/asia.201601722
Chemistry - An Asian Journal
FULL PAPER
Figure 2. Absorption spectra of the diacetylene monomer MA164 and the
cross-linked MA164 after photopolymerization (MA164 AP).
Table 1. Optical and electrochemical data of MA164 and MA164 AP
[d]
λabs nm (104
M-1cm-1)[a]
E (S+/S)
E0-0
E (S+/S*)
Dye
Egap V
V[a]
V [b]
V [c]
Figure 3. a) Photocurrent-voltage curves with DSSCs based on the
diacetylene monomer MA164 and the cross-linked MA164 AP obtained from
the same cell, under illumination and in the dark. b) The IPCE (%) plots.
406 (2.00),
481 (2.78)
MA164
MA164 AP
1.09
2.22
-
-1.13
-
0.63
-
405 (2.10),
481 (2.91)
Table 2. DSSC performance parameters of dyes[a]
Dye
JSC[mAcm-2]
VOC[V]
FF
η (%)
[a] Data were measured in DMF solution. [b] E0-0 value was estimated from
the intersection of the normalized absorption and emission spectra. [c] E
(S+/S*) was calculated from E (S+/S) – E0-0. [d] Energy gap between the
excited-state oxidation potential and TiO2 conduction band edge.
MA164
MA164 AP
CR147
N719
13.5
14.9
13.6
14.9
0.728
0.750
0.711
0.797
0.73
0.74
0.73
0.72
7.17
8.27
7.05
8.41
To further confirm the formation of cross-linked dye
assemblies upon photoirradiation and the effect on the electrode
surface, the diacetylene monomers adsorbed on the TiO2
surface were subjected to UV-irradiation at room temperature.
After one-hour UV-irradiation, the cross-linked dye assemblies
were desorbed from TiO2 and the molecular weight distribution
was determined by gel permeation chromatography (GPC). The
GPC analysis revealed that the cross-linked dye assemblies
contain predominant hexamers with a narrow polydispersity
index (Mw/Mn) of 1.02. The hydrophobicity of the monomer dyes
and the cross-linked dye assemblies coated on a 12 µm TiO2
film were evaluated by the water contact angle measurements.
The static contact angle values averaged out of 10
measurements were found to be 127° and 134° for monomer
dyes and the cross-linked dye assemblies, respectively, which
confirms the enhancement of hydrophobicity of TiO2 film upon
photoinduced cross-linking of the monomer dyes.
[a] Cells composed of 12 µm thick transparent TiO2 layer with a scattering
layer 4 µm in thickness. Working area of 0.20 cm2. Electrolyte: SOLARONIX,
Iodolyte HI-30. Dye bath: 0.3 mM dye in dichloromethane.
Photovoltaic performance
The DSSCs with diacetylene monomer MA164 and cross-linked
MA164 AP as the sensitizers were fabricated and subjected to the
performance measurements. The devices with N719 and CR147
dyes[19] were also prepared as references for comparison. The
photovoltaic performance parameters of all the devices tested under
standard conditions (AM 1.5 G, 100 mW/cm2) are collected in Table
2.
Figure 3a shows the photocurrent-voltage (J-V) plots under
illumination and in the dark. The MA164 sensitized cell gave a
JSC of 13.5 mAcm-2, a VOC of 0.729 V, and a fill factor (FF) of
0.73, which correspond to an overall conversion efficiency (η) of
7.17%. Remarkably, the cell sensitized with cross-linked MA164
AP generated from post UV treatment of MA164 adsorbed on
TiO2 gave a JSC of 14.9 mAcm-2, a VOC of 0.75 V, and a FF of
Table 1 summarizes the photophysical and electrochemical
data of all dyes investigated in this work. It is clear that both driving
forces for charge injection from photoexcited dyes to the
conduction band of TiO2 as well as the dye regeneration from
redox mediators to oxidized dyes are thermodynamic feasible.[18]
For internal use, please do not delete. Submitted_Manuscript
This article is protected by copyright. All rights reserved.

10.1002/asia.201601722
Chemistry - An Asian Journal
FULL PAPER
0.74, which correspond to an efficiency of 8.27%. Under the
same conditions, the CR147 sensitized cell gave a JSC of 13.6
mAcm-2, a VOC of 0.711 V, and a FF of 0.73, which correspond to
η = 7.05%. The most striking feature is that the DSSCs based on
indicative of more effective suppression of the dark current in the
cross-linked MA164 AP sensitized cell as a result of efficient
shielding effect of cross-linked hydrophobic PDA layer from the
approaching of oxidized redox mediators.
the cross-linked dye exhibited higher VOC
JSC values than
and
both the diacetylene monomer MA164 and the reference dye
CR147. significant improvement in the incident
Additional evidence for the slower charge recombination
kinetics is provided by the plots of the electron lifetimes as a
function of VOC measured by the intensity modulated
A
monochromatic photon-to-current conversion efficiency (IPCE)
was observed in the cell photosensitized by the cross-linked
MA164 AP in the entire visible region (Figure 3b). The effective
energy transfer from the PDA network to dipolar dyes, which
accounts for the photocurrent enhancement, was confirmed by
the fluorescence titration experiment as shown in Figure S3.
photovoltage spectroscopy as shown in Figure 4c. At fixed VOC
,
the electron lifetime of the cell sensitized by cross-linked MA164
AP is longer than that of the monomer MA164 indicative of
suppressed charge recombination in MA164 AP-based cell,
which is consistent with the observed VOC. The cross-linked
chain could also capable of suppressing the dye aggregation
and generate poly-anchoring supramolecular assemblies on the
TiO2 surface, which is beneficial for long-term stability.
Generally, an increase in VOC can be achieved by an
upward shift of the conduction band edge of TiO2 or suppression
of charge recombination between the injected electrons in TiO2
and the oxidized redox species.[20] Charge extraction
experiments were employed to measure the charge and electron
density at the TiO2 electrode as a function of voltage. The results
are depicted in Figure 4a. The higher charge accumulation in the
cell sensitized by cross-linked MA164 AP indicates a 60 mV
downward shift of the TiO2 conduction band edge with respect to
the cell sensitized by MA164. The result of downward shift is
indeed in contrast to the increase in the Voc of cell sensitized by
cross-linked MA164 AP.
Further support for the effective suppression of the dark
current is illustrated in Figure 4d by electrochemical impedance
spectra (EIS) (diacetylene-based MA164 vs. polydiacetylene-
based MA164 AP) generated from the same cell. The Nyquist
plots under dark condition displayed larger electron
recombination resistance (Rrec) in the cell sensitized with cross-
linked MA164 AP than that with diacetylene monomer MA164.
The results suggest that the electron recombination rate is
relatively slower for the polymer dyes compared to the monomer.
Thus, the cross-linked hydrophobic shell effectively inhibits back
electron transfer from TiO2 to I3- ions and results in a higher VOC
.
The characteristic frequency peaks (inverse of the
recombination lifetime in the TiO2 film) in the Bode phase shown
in Figure S4 shifted to a lower frequency for MA164 AP based
device.
Figure 5 shows the long-term stability test for DSSCs based
on MA164 and CR147 under continuous light soaking (100
mW/cm2) at 70 °C. The PCE in MA164 maintained above 96%
of the initial value after 600 h light soaking at a harsh condition
while CR147 started decreasing after 500 h, demonstrating the
merit of crosslinking on the long-term stability of the devices
under long-term photoirradiation.
Figure 4. a) VOC as a function of the charge density of DSSCs based on
charge extraction technique. b) VOC as a function of Electron lifetime c)
Electron lifetime against the electron density of DSSCs based on IMVS studies.
(D) ESI (Nyquist plots) of DSSCs measured in the dark under 0.45 V bias.
In order to rationalize the enhancement of the photovoltage
of cross-linked MA164 AP sensitized DSSC, the electron
recombination losses from the TiO2 to the electrolyte was
examined by ploting the charge density at open circuit potential
as a function of electron lifetime (Figure 4b). At a fixed charge
density (Q), the electron lifetime for the cross-linked MA164 AP
is 10-fold higher than the diacetylene monomer MA164, clearly
For internal use, please do not delete. Submitted_Manuscript
This article is protected by copyright. All rights reserved.

10.1002/asia.201601722
Chemistry - An Asian Journal
FULL PAPER
m-2) white light emitting diode. The frequency range was set from 1 kHz
to 100 mHz.
Figure 5. Long-term stability test for DSSCs based on MA164 and CR147 and
electrolyte (SOLARONIX, Iodolyte Z-150) under light soaking (100 mW/cm2) at
70 °C.
Device Fabrication and Photopolymerization
Conclusions
Fluorine-doped tin oxide (FTO) glass plates were pre-cleaned
sequentially by sonicating in acetone bath, detergent, DI-water and
isopropanol at room temperature, each for 15 min. The FTO sheets were
subsequently pretreated with 40 mM Aquarius TiCl4 solution at 70 °C for
60 min then washed with DI-water and ethanol. Afterwards, the coated
FTO substrate was heated at 480 °C for 40 min on which the 12 µm
transparent nanocrystalline TiO2 layer in direct contact with the FTO
substrate was deposited using a doctor-blade technique. Then, the TiO2
films were heated at 480 °C for 40 min. The processes was repeated to
introduce 4 µm thickness of light scattering TiO2 particle. The thickness
of TiO2 films was measured by veeco dektak 150 surface profilometer.
The annealed TiO2 electrodes were immersed in DCM containing 0.3 mM
photosensitizer (MA164, CR147 and N719) for 24 h at room temperature.
The active area of all DSSCs is 0.20 cm2. Pt counter electrodes were
prepared by spreading a droplet of 5 mM H2PtCl6 in ethanol on top of a
FTO substrate, wiped with smooth paper to make it uniform and was
heated at 500 °C for 60 min for deposition of platinum. The two
electrodes were sealed with 30 mm thick thermoplastic Surlyn (Solaronix)
and the redox electrolyte (Iodolyte HI-30 purchased from SOLARONIX)
was injected through a hole drilled in the counter electrode. The two
holes on the counter electrode were sealed once again with 30 mm thick
Surlyn and microscope slide. After recording all the performance
measurements based on the monomeric MA164, the assembled cell
were subjected into a photochemical reactor PR-2000 to generate its
corresponding cross-linked MA164 AP. All the performance
measurements of MA164 and MA164 AP were generated from the same
cells.
A new organic dye with photoinduced cross-linking shell as the
hydrophobic electrolyte-blocking layer has been designed and
successfully synthesized. The resulting polydiacetylene network
is demonstrated to be an effective strategy for blocking the
oxidized redox mediator approaching the TiO2 surface and thus
can be applied in any sensitizers for DSSCs to achieve higher
VOC as well as JSC by minimizing the charge recombination and
providing additional light harvesting. Up to 15% efficiency
enhancement for cross-linked MA164 AP sensitized cell is
achieved. In addition, the cross-linked diacetylene network is
believed to provide enhanced stability due to the multiple
anchoring groups in each dye assemblies. The current work
provides a proof-of-concept structural design of efficient organic
sensitizers and could in principle be applied to many other
sensitizers.
Experimental Section
General remarks: All chemical reagents were purchased from
commercial sources and used without further purification unless specified.
All solvents used were carefully dried and freshly distilled according to
standard laboratory practices. All manipulations were carried out under
inert nitrogen atmosphere. All reactions were monitored using pre-coated
TLC plates and purified by column chromatography. Column
chromatography was performed on silica (60-120 mesh). Absorption and
fluorescence spectra were obtained with a Varian Cary 300 UV-vis
spectrophotometer and a Jobin-Yvon FL3-21 Horiba fluorolog fluorimeter,
respectively. 1H and 13C NMR spectra were recorded on a Brüker
AVANCE III 400 MHz, Ultra Shield 400 MHz instruments. The HRMS
were conducted on an Applied Biosystems 4800 Proteomics Analyzer
equipped with an Nd/YAG laser (335 nm) operating at a repetition rate of
200 Hz. Cyclic voltammetry (CV) were carried out on CHI Model 621B
Electrochemical Analyzer with a three-electrode configuration consisting
of a platinum working electrode, a platinum wire auxiliary electrode, and
a non-aqueous Ag/AgNO3 reference electrode. The experiments were
Long-term stability data of a DSSC based on MA164 and CR147 and
electrolyte (SOLARONIX, Iodolyte Z-150) under the irradiance of AM 1.5
G full sun visible light soaking at 70 °C. Atlas Suntest CPS+ Xenon Test
Instrument use air-cooled xenon lamps to simulate UV and visible solar
radiation. The cells were covered with a black mask with an aperture size
of 0.25 cm2 and UV light filter glass. Prior to measurements the
sensitized cells were cooled to room temperature.
Synthesis
1-(bromomethyl)-4-iodobenzene (2). N-bromosuccinimide (3.6 g, 20.22
mmol) and dibenzyol peroxide (0.14 g, 0.4 mmol) was added to a
solution of 4-iodotoluene (1) (4.06 g, 18.6 mmol) dissolved in 40 mL of
anhydrous carbon tetrachloride and refluxed overnight. Afterwards the
reaction mixture was filtered and the solvent removed under reduced
performed in degassed DMF containing 0.1
M tetrabutylammonium
hexafluorophosphate and 1.0 mM of the analyte. The potentials were
quoted against the ferrocene/ferrocenium (Fc/Fc+) redox couple as the
internal standard and converted to NHE by addition of 0.63 V. Contact
angles were measured by the sessile drop method using a GBX Digidrop
pressure to give
a residual solid, which was purified by column
chromatography using hexane/DCM as eluent affording the target
product as an off-white solid (4.7 g, 85%). 1H NMR (400 MHz, CDCl3): δ
ppm, 7.68 (d, 2H, J = 8.4 Hz), 7.13 (d, 2H, J = 8.4 Hz), 4.42 (s, 2H).
contact angle meter equipped with
a CCD camera. The reported
experimental values are averages of at least five measurements
performed on different parts of each TiO2 coated sample. The static
contact angle values are the average of 10 measurements and the drop
size as small as (1 µL); hence the gravitational force is neglected.
Photocurrent-voltage characteristics of the DSSCs were recorded with
LSQE-IV Class AAA solar simulator (SAN-EL ELECTRIC Co., Ltd.) at a
light intensity of 100 mW/cm2 calibrated by an Oriel reference solar cell
(Oriel 91150, Newport®). Electrochemical impedance spectra (EIS) were
(4-(4-iodophenyl)but-1-yn-1-yl)trimethylsilane (3). A two-necked round
bottom flask charged with trimethyl(prop-1-yn-1-yl)silane (2.94 mL, 19.8
mmol) in THF (30 mL) was cooled to -78 °C and kept under nitrogen
atmosphere. Then n-BuLi (13.6 mL, 21.8 mmol) was added drop-wise
and the resulting solution was slowly allowed to warm to -20 °C in 1 h. A
solution of compound 2 (5 g, 15.2 mmol) in THF (20 mL) was then added
slowly via syringe and the reaction mixture was allowed to stir at room
temperature for 12 h. The reaction was quenched with water (100 mL),
extracted with DCM (3 × 50 mL), and dried over anhydrous MgSO4. The
filtrate was concentrated and flashed with silica gel chromatography
recorded for DSSCs in dark at −0.45
V bias potential at room
temperature. Intensity-modulated photovoltage spectroscopy (IMVS) was
carried out on the electrochemical workstation (Zahner, Zennium) with a
frequency response analyzer under an intensity modulated (10 to 300 W
For internal use, please do not delete. Submitted_Manuscript
This article is protected by copyright. All rights reserved.

10.1002/asia.201601722
Chemistry - An Asian Journal
FULL PAPER
(hexane/DCM) to afford a light yellow oil (4.1 g, 82%). 1H NMR (400 MHz,
CDCl3): δ ppm, 7.62 (d, J = 8.1 Hz, 2H), 6.98 (d, J = 8.1 Hz, 2H), 2.77 (t,
J = 7.4 Hz, 2H), 2.48 (t, J = 7.4 Hz, 2H), 0.1 (s, 9H) . 13C NMR (100 MHz,
CDCl3): δ ppm, 140.1, 137.2, 130.6, 106.0, 91.5, 85.7, 34.4, 21.9, 0.04.
(400 MHz, CDCl3): δ ppm, 8.10 (d, J = 7.6 Hz, 1H), 7.72-7.68 (m, 5H),
7.57 (t, J = 8 Hz, 2H), 7.40-7.14 (m, 16H), 7.05 (t, J = 7.6 Hz, 1H), 2.83 (t,
J = 7.4 Hz, 2H), 2.51 (t, J = 7.6 Hz, 2H), 0.16 (s, 9H). 13C NMR (100 MHz,
CDCl3): δ ppm, 152.7, 152.4, 147.8, 147.7, 145.8, 139.7, 139.3, 138.7,
138.6, 138.5, 135.7, 133.0, 131.6, 130.9, 130.2, 130.1, 129.5, 129.3,
129.1, 128.3, 128.2, 125.0, 124.7, 123.0, 122.4, 122.2, 106.7, 85.4, 34.5,
29.7, 22.2, 0.10. HRMS (FAB) m/z: [M+H]+ calcd for C45H38BrN3Si,
730.2080; found, 730.2067.
N,N-diphenyl-4-(4-(trimethylsilyl)but-3-yn-1-yl)aniline (4). Compound
3 (4.0 g, 12.18 mmol), diphenylamine (1.72 g, 10.15 mmol), palladium
acetate (0.109 g, 0.49 mmol), toluene (40 mL), tri-tert-butylphosphine
(0.124 g, 0.61 mmol) and sodium tert-butoxide (3.5 g, 36 mmol) were
placed in a two-necked round bottom flask under N2 atmosphere and the
mixture was heated at 90°C for 16 h. The reaction solution was cooled to
room temperature and poured into water (150 mL). The mixture was
extracted with CH2Cl2. Solvent was removed under reduced pressure.
The resulting light yellowish oil was purified by column chromatography
(silica gel, hexane/DCM) to give compound 4 as a dark green, viscos oil
(3.75 g, 67%). 1H NMR (400 MHz, CDCl3): δ ppm, 7.23 (t, J = 7.8 Hz, 4H),
7.11-7.06 (m, 6H), 7.03-6.98 (m, 4H), 2.79 (t, J = 7.6 Hz, 2H), 2.50 (t, J =
7.6 Hz, 2H), 0.15 (s, 9H). 13C NMR (100 MHz, CDCl3): δ ppm, 147.9,
146.1, 135.2, 129.4, 129.1, 124.4, 123.8, 122.4, 106.7, 85.4, 34.4, 22.2,
0.1. HRMS (FAB) m/z: [M+H]+ calcd for C25H27NSi, 369.1907; found,
369.1898.
4-(8-bromo-2,3-diphenylquinoxalin-5-yl)-N-(4-(4-bromobut-3-yn-1-
yl)phenyl)-N-phenylaniline (8). A solution of dry acetone (20 mL)
containing compound 7 (0.90 g, 1.24 mmol), N-bromosuccinimide (0.178
g, 1 mmol), and silver nitrate (63 mg, 0.37 mmol) was stirred at room
temperature for 4 h. The solvent was removed in vacuo and the resulting
product was dissolved in DCM and passed through a short silica gel
column to afford compound 8 as an orange red solid (0.82 g, 89%). 1H
NMR (400 MHz, CDCl3): δ ppm, 8.10 (d, J = 7.6 Hz, 1H), 7.72-7.67 (m,
5H), 7.58-7.56 (m, 2H), 7.57 (t, J = 9.2 Hz, 2H), 7.40-7.12 (m, 16H), 7.04
(t, J = 7.2 Hz, 1H), 2.83 (t, J = 7.6 Hz, 2H), 2.52 (t, J = 7.6 Hz, 1H).
HRMS (FAB) m/z: [M+H]+ calcd for C42H29Br2N3, 733.0785; found,
733.0776.
4-bromo-N-phenyl-N-(4-(4-(trimethylsilyl)but-3-yn-1-yl)phenyl)aniline
(5). N-bromosuccinimide (1.52 g, 8.6 mmol) was added at once in dark to
a solution of compound 4 (3 g, 8.11 mmol) dissolved in 30 mL
chloroform and stirred at room temperature for 12 h. The mixture was
poured into water (100 mL) and extracted with DCM (3 × 50 mL). The
combined organic layers were washed with water and dried over
anhydrous sodium sulfate. Solvent was removed under reduced pressure.
The resulting viscos oil was purified by column chromatography (silica
gel, hexane/DCM) to give compound 5 (3.02 g, 83%). 1H NMR (400 MHz,
CDCl3): δ ppm, 7.31-7.24 (m, 4H), 7.22-7.05 (m, 7H), 7.01-6.91 (m, 2H),
2.79 (t, J = 7.6 Hz, 2H), 2.50 (t, J = 7.6 Hz, 2H), 0.14 (s, 9H). 13C NMR
(100 MHz, CDCl3): δ ppm 147.4, 147.1, 145.5, 135.8, 132.1, 129.5, 129.3,
124.8, 124.6, 124.2, 123.0, 114.4, 106.6, 85.5, 34.4, 22.2, 0.1. HRMS
(FAB) m/z: [M+H]+ calcd for C25H26BrNSi, 447.1012; found, 447.1014.
4-(8-bromo-2,3-diphenylquinoxalin-5-yl)-N-(4-(8-methylnona-3,5-
diyn-1-yl)phenyl)-N-phenylaniline (9). CuCl (10.6 mg, 0.11 mmol) was
added to a 30% n-BuNH2 (5 mL) aqueous solution at room temperature
that resulted in the formation of a blue solution immediately. A few
crystals of hydroxylamine hydrochloride were added to discharge the
blue color. The resulting colorless solution indicated the formation of
Cu(I) salt. Subsequently, 4-methylpent-1-yne (264 mg, 3.21 mmol) was
added to the solution at room temperature to form a yellow acetylide
suspension that was immediately cooled down with an ice-water bath.
The solution of compound 8 (0.787 g, 1.07 mmol) in DCM was added at
once and the ice bath was removed. After 6 h of stirring at room
temperature, the reaction was finished according to TLC. The product
was diluted with water and repeatedly extracted with DCM, dried over
MgSO4, concentrated with reduced pressure and the crude product was
further purified by flash column chromatography on silica gel to afford the
title product as an orange red solid (0.64 g, 81%). 1H NMR (400 MHz,
CDCl3): δ ppm, 8.10 (d, J = 8.0 Hz, 1H), 7.71-7.67 (m, 5H), 7.56 (t, J =
8.4 Hz, 2H), 7.39-7.12 (m, 16H), 7.05 (t, J = 7.6 Hz, 1H), 2.84 (t, J = 7.6
Hz, 2H), 2.57 (t, J = 7.6 Hz, 2H), 2.16 (d, J = 6.4 Hz, 2H), 1.87-1.84 (m,
1H), 0.99 (d, J = 6.8 Hz, 6H). 13C NMR (100 MHz, CDCl3): δ ppm, 152.7,
152.4, 147.8, 147.7, 145.9, 139.7, 139.3, 138.7, 138.6, 135.3, 133.0,
131.6, 130.9, 130.2, 130.1, 129.5, 129.3, 129.1, 128.3, 128.2, 125.0,
124.7, 123.0, 122.4, 122.3, 76.5, 68.0, 66.1, 66.0, 34.2, 28.4, 28.0, 25.6,
22.0, 21.5. HRMS (FAB) m/z: [M+H]+ calcd for C48H38BrN3, 736.2322;
found, 736.2350.
N-phenyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-N-(4-(4-
(trimethylsilyl)but-3-yn-1-yl)phenyl)aniline (6). Compound 5 (3 g, 6.69
mmol), bis(pinacolato)diborane (2.0 g, 8 mmol), (dppf)PdCl2 (0.25 g, 0.34
mmol), and KOAc (1.97 g, 20.0 mmol) were kept in a two necked-round
bottom flask under N2 atmosphere and dissolved in 30 mL degassed
dioxane. The reaction mixture was stirred at 80 °C for 24 h. Afterwards
the solution was cooled to room temperature, poured into 100 mL water
and extracted with DCM (3x 50 mL). The organic phase was collected,
dried over magnesium sulfate and evaporated the solvent. The residue
was subjected to silica gel column chromatography to obtain the desired
product as light green solid (2.22 g, 67%). 1H NMR (400 MHz, CDCl3): δ
ppm, 7.66 (d, J = 8.4 Hz, 2H), 7.24 (d, J = 7.6 Hz, 2H), 7.10 (t, J = 11 Hz,
4H), 7.04-6.99 (m, 5H), 2.79 (t, J = 7.6 Hz, 2H), 2.50 (t, J = 7.6 Hz, 2H),
1.33 (s, 12H), 0.14 (s, 9H). 13C NMR (100 MHz, CDCl3): δ ppm, 150.7,
147.5, 145.6, 135.8, 129.5, 129.3, 125.1, 124.8, 123.2, 121.5, 106.7,
85.4, 83.5, 34.5, 24.9, 22.2, 0.10. HRMS (FAB) m/z: [M+H]+ calcd for
C31H38BNO2Si, 495.2759; found, 495.2752.
5-(8-(4-((4-(8-methylnona-3,5-diyn-1-
yl)phenyl)(phenyl)amino)phenyl)-2,3-diphenylquinoxalin-5-
yl)thiophene-2-carbaldehyde (10). A degassed solution of THF (10 mL)
and H2O (5 mL) was added into a round bottom flask containing
compound 9 (0.60 g, 0.814 mmol), 5-formyl-2-thiopheneboronic acids
(0.156 g, 1 mmol), Na2CO3 (0.53 g, 5 mmol), and Pd(PPh3)2Cl2 (0.035 g,
0.05 mmol). The resulting mixture was stirred for 12 h at 50°C under N2
atmosphere. The mixture was extracted with DCM, dried over anhydrous
4-(8-bromo-2,3-diphenylquinoxalin-5-yl)-N-phenyl-N-(4-(4-
MgSO , and purified by column chromatography (gradients of
4
(trimethylsilyl)but-3-yn-1-yl)phenyl)aniline (7). A degassed solution of
THF (20 mL) and H2O (10 mL) was added to a flask containing the
compound 6 (1.5 g, 3 mmol), 5,8-dibromo-2,3-diphenylquinoxaline (1.33
g, 3 mmol), Na2CO3 (1.6 g, 15 mmol), and Pd(PPh3)2Cl2 (0.105 g, 0.15
mmol). The resulting mixture was stirred for 6 h at 50°C under a N2
atmosphere. The mixture was extracted with DCM, dried over MgSO4,
and purified by column chromatography with hexane/DCM as the eluent
to yield the desired compound 7 as a yellow solid (1.51 g, 69%). 1H NMR
hexane/DCM as the eluent) to yield the desired product as a red solid
(0.444 g, 71%). 1H NMR (400 MHz, CDCl3): δ ppm, 9.99 (s, 1H), 8.25 (d,
J = 8.0 Hz, 1H), 7.94 (d, J = 8.0 Hz, 1H), 7.88 (d, J = 8.0 Hz, 1H), 7.82 (d,
J = 8.0 Hz, 1H), 7.78-7.73 (m, 5H), 7.61 (d, J = 7.2 Hz, 2H), 7.43-7.14 (m,
15H), 7.07 (t, J = 7.2 Hz, 1H), 2.84 (t, J = 7.6 Hz, 2H), 2.57 (t, J = 7.6 Hz,
2H), 2.16 (d, J = 6.8 Hz, 2H), 1.87-1.80 (m, 1H), 0.99 (d, J = 6.8 Hz, 6H).
13C NMR (100 MHz, CDCl3): δ ppm, 183.3, 151.8, 148.7, 147.9, 147.6,
For internal use, please do not delete. Submitted_Manuscript
This article is protected by copyright. All rights reserved.

10.1002/asia.201601722
Chemistry - An Asian Journal
FULL PAPER
145.9, 144.9, 140.6, 138.8, 138.6, 138.4, 137.5, 135.6, 135.4, 131.7,
131.0, 130.3, 130.1, 129.7, 129.3, 129.0, 128.4, 128.2, 126.9, 125.3,
125.1, 124.8, 124.7, 123.2, 123.0, 122.2, 121.9, 110.3, 76.5, 66.1, 66.0,
34.2, 29.7, 28.4, 28.0, 22.0. HRMS (FAB) m/z: [M+H]+ calcd for
C53H41N3OS, 768.3043; found, 768.3050.
C. O’Regan, R. Humphry-Baker and M. Grätzel, J. Phys. Chem. B,
2005, 109, 21818.
[8]
[9]
a) E. Palomares, J. N. Clifford, S. A. Haque, T. Lutz and J. R. Durrant,
Chem. Commun., 2002, 1464; b) E. Palomares, J. N. Clifford, S. A.
Haque, T. Lutz and J. R. Durrant, J. Am. Chem. Soc., 2003, 125, 475.
a) S. Handa, S. A. Haque and J. R. Durrant, Adv. Funct. Mater., 2007,
17, 2878; b) H. Choi, S. Kang, J. Ko, G. Gao, H. Kang, M.-S. Kang, Md.
K. Nazeeruddin and M. Grätzel, Angew. Chem. Int. Ed., 2009, 48, 5938.
Synthesis of the diacetylene monomere, MA164. Compound 10 (0.23
g, 0.30 mmol), cyanoacetic acid (0.128 g, 1.5 mmol) and ammonium
acetate (0.023 g, 0.30 mmol) was introduced into an aluminum foil
covered two necked round bottom flask containing a mixture of glacial
acetic acid/THF (5:2, 7 mL) under N2 atmosphere and heated at 80 °C for
24 h. After cooling, the resulting precipitate was filtered, washed several
times with water and a mixture of hexane and DCM. The residue was
dried under high vacuum to yield the product as a dark red powder (0.21
g, 84%). 1H NMR (400 MHz, CDCl3): δ ppm, 8.4 (s, 1H), 8.26 (d, J = 8.0
Hz, 1H), 7.79-7.75 (m, 5H), 7.63 (d, J = 7.2 Hz, 2H), 7.48 (t, J = 7.2 Hz,
2H), 7.44-7.42 (m, 3H), 7.35-7.05 (m, 14H), 2.84 (t, J = 7.4 Hz, 2H), 2.57
(t, J = 7.4 Hz, 2H), 2.16 (d, J = 6.4 Hz, 2H), 1.87-1.80 (m, 1H), 0.99 (d, J
= 6.4 Hz, 6H). 13C NMR (100 MHz, CDCl3): δ ppm, 167.3, 152.3, 152.1,
150.2, 148.1, 148.0, 147.6, 145.8, 140.9, 138.7, 138.5, 138.1, 138.0,
137.2, 131.7, 130.8, 130.5, 130.1, 129.3, 129.0, 128.9, 128.7, 128.2,
128.0, 126.9, 125.3, 125.1, 124.9, 124.7, 123.2, 122.0, 121.8, 115.8,
96.2, 66.2, 66.0, 34.2, 29.7, 28.4, 28.0, 22.0, 21.5. HRMS (FAB) m/z:
[M+H]+ calcd for C56H42N4O2S, 835.3101; found, 835.3139.
[10] a) N. Satoh, T. Nakashima and K. Yamamoto, J. Am. Chem. Soc., 2005,
127, 13030; b) T. Nakashima, N. Satoh, K. Albrecht and K. Yamamoto,
Chem. Mater., 2008, 20, 2538.
[11] a) N. Koumura, Z.-S. Wang, S. Mori, M. Miyashita, E. Suzuki and K.
Hara, J. Am. Chem. Soc., 2006, 128, 14256; b) S. Ito, H. Miura, S.
Uchida, M. Takata, K. Sumioka, P. Liska, P. Comte, P. Pechy and M.
Grätzel, Chem. Commun., 2008, 41, 5194; c) Z.-S. Wang, N.
Koumura, Y. Cui, M. Takahashi, H. Sekiguchi, A. Mori, T. Kubo, A.
Furube and K. Hara, Chem. Mater., 2008, 20, 3993; d) K.-F. Chen,
Y.-C. Hsu, Q. Wu, M. C.-P. Yeh, S-S. Sun, Org. Lett., 2009, 11, 377;
e) K.-F. Chen, C.-W. Chang, J.-L. Lin, Y.-C. Hsu, Q. Wu, M. C.-P.
Yeh, C.-P. Hsu, S-S. Sun, Chem. Eur. J., 2010, 16, 12873; f) Z.
Ning, Y. Fu and H. Tian, Energy Environ. Sci., 2010, 3, 1170; g) J.
Xu, H. Wu, X. Jia and D. Zou, Chem. Commun., 2012, 48, 7793; h)
C. Lan, H. Wu, T. Pan, C. Chang, W. Chao, C. Chen, C. Wang, C.
Lin and E. W. Diau, Energy Environ. Sci., 2012, 5, 6460; i) S. Qu, C.
Qin, A. Islam, Y. Wu, W. Zhu, J. Hua, H. Tian and L. Han, Chem.
Commun., 2012, 48, 6972; j) R. Agosta, R. Grisorio, L. De Marco, G.
Romanazzi, G. P. Suranna, G. Gigli and M. Manca, Chem.
Commun., 2014, 50, 9451; k) X. Sun, Y.-Q. Wang, X. Li, H. Ågren,
W.-H. Zhu, H. Tian and Y.-S. Xie, Chem. Commun., 2014, 50,
15609.
Acknowledgements
We are grateful to the Ministry of Science and Technology of
Taiwan (Grant No MOST 103-2113-M-001-026-MY3) and
Academia Sinica for support of this research. MAD thanks
Taiwan International Graduate Program of Academia Sinica for
the fellowship support. Mass spectrometry analyses were
performed by Mass Spectrometry facility of the Institute of
Chemistry, Academia Sinica.
[12] J.-Y. Su, C.-H. Tsai, S.-A. Wang, T.-W. Huang, C.-C. Wu and K.-T.
Wong, RSC Adv., 2012, 2, 3722.
[13] a) T. Kim, R. M. Crooks, M. Tsen and L. Sun, J. Am. Chem. Soc., 1995,
117, 3963; b) H. Menzel, M. D. Mowery, M. Cai and C. E. Evans, Adv.
Mater., 1999, 11, 131; c) D. H. Charych, J. O. Nagy, W. Spevak and M.
D. Bednarski, Science, 1993 , 261, 585; d) J. Tsibouklis, Adv. Mater.
1995, 7, 407; e) N. Fujita, Y. Sakamoto, M. Shirakawa, M. Ojima, A.
Fujii, M. Ozaki and S. Shinkai, J. Am. Chem. Soc., 2007, 129, 4134.
[14] M. I. Mangione and R. A. Spanevello, Macromolecules, 2013, 46, 4754.
[15] J. A. Bergman, K. Hahne, J. Song, C. A. Hrycyna, and R. A. Gibbs,
ACS Med. Chem. Lett., 2012, 3, 15.
Keywords: Dark current suppression • Diacetylene • Dye-
sensitized solar cell • Hydrophobic electrolyte-blocking layer •
Polymerization • Sensitizers
[16] a) B. Tieke, G. Wegner, D. Naegele and H. Ringsdorf, Angew. Chem.,
Int. Ed., 1976, 15, 764; b) B. Tieke, H.-J. Graf, G. Wegner, B. Naegele,
H. Ringsdorf, A. Banerjie, D. Day and J. B. Lando, Colloid Polym. Sci.,
1977, 255, 521.
[1]
[2]
B. O’Regan and M. Grätzel, Nature, 1991, 353, 737.
S. Mathew, A. Yella, P. Gao, R. Humphry-Baker, B. F. E. Curchod, N.
Ashari-Astani, I. Tavernelli, U. Rothlisberger, M. K. Nazeeruddin and M.
Grätzel, Nat. Chem., 2014, 6, 242.
[17] a) D. J. Ahn and J.-M. Kim, Acc. Chem. Res., 2008, 41, 805; b) C. Zhu,
L. Liu, Q. Yang, F. Lv and S. Wang, Chem. Rev., 2012, 112, 4687; c) B.
Yoon, S. Lee and J.-M. Kim, Chem. Soc. Rev., 2009, 38, 1958; d) X.
Sun, T. Chen, S. Huang, L. Li and H. Peng, Chem. Soc. Rev., 2010, 39,
4244.
[3]
[4]
Z. Yao, H. Wu, Y. Li, J. Wang, J. Zhang, M. Zhang, Y. Guo and P.
Wang, Energy Environ. Sci., 2015, 8, 3192.
C. Y. Chen, M. Wang, J. Y. Li, N. Pootrakulchote, L. Alibabaei, C. H.
Ngocle, J. D. Decoppet, J. H. Tsai, C. Grätzel, C. G. Wu, S. M.
Zakeeruddin and M. Grätzel, ACS Nano, 2009, 3, 3103.
a) A. Hagfeldt, G. Boschloo, L. Sun, L. Kloo and H. Pettersson, Chem.
Rev., 2010 , 110, 6595; b) C.-P. Lee, Ryan Y.-Y. Lin, L.-Y. Lin, C.-T.
Li, T.-C. Chu, S.-S. Sun, J.-T. Lin and K.-C. Ho, RSC Adv., 2015, 5,
23810.
[18] A. Hagfeldt and M. Grätzel, Chem. Rev., 1995, 95, 49.
[19] a) S.-R. Li, C.-P. Lee, H.-T. Kuo, K.-C. Ho and S.-S. Sun, Chem. Eur. J.,
2012, 18, 12085; b) S.-R. Li, C.-P. Lee, P.-F. Yang, C.-W. Liao, M. M.
Lee, W.-L. Su, C.-T. Li, H.-W. Lin, K.-C. Ho and S.-S. Sun, Chem. Eur.
J., 2014, 20, 10052; c) S.-R. Li, C.-P. Lee, C.-W. Liao, W.-L. Su, C.-T.
Li, K.-C. Ho and S.-S. Sun, Tetrahedron, 2014, 70, 6276; d) C.-T. Li,
C.-P. Lee, C.-T. Lee, S.-R. Li, S.-S. Sun, K.-C. Ho, ChemSusChem,
2015, 8, 1244.
[5]
[6]
[7]
K. Kakiage, Y. Aoyama, T. Yano, K. Oya, J. Fujisawa and M. Hanaya,
Chem. Commun., 2015, 51, 15894.
[20] M. Xu, M. Zhang, M. Pastore, R. Li, F. D. Angelis and P. Wang, Chem.
Sci., 2012, 3, 976.
a) B. C. O’Regan, S. Scully, A. C. Mayer, E. Palomares and J. Durrant,
J. Phys. Chem. B, 2005, 109, 4616; b) Z. Zhang, S. M. Zakeeruddin, B.
For internal use, please do not delete. Submitted_Manuscript
This article is protected by copyright. All rights reserved.

10.1002/asia.201601722
Chemistry - An Asian Journal
FULL PAPER
Entry for the Table of Contents (Please choose one layout)
Layout 1:
FULL PAPER
Mekonnen Abebayehu Desta, Chia-Wei
Liao and Shih-Sheng Sun*
Text for Table of Contents
Page No. – Page No.
A General Strategy to Enhance the
Performance of Dye-sensitized Solar
Cells
by
Incorporating
Light-
harvesting Dye with Hydrophobic
Polydiacetylene Electrolyte-blocking
Layer
For internal use, please do not delete. Submitted_Manuscript
This article is protected by copyright. All rights reserved.