Research Article

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Fused Fluorenylindolenine-Donor-Based Unsymmetrical Squaraine

Dyes for Dye-Sensitized Solar Cells
Rajesh Bisht,†,§ Vediappan Sudhakar,‡,§ Munavvar Fairoos Mele Kavungathodi,† Neeta Karjule,†,§
and Jayaraj Nithyanandhan*,†,§
†
Physical and Materials Chemistry Division and ‡Polymer Science and Engineering Division, CSIR-National Chemical Laboratory,
CSIR-Network of Institutes for Solar Energy, Dr. Homi Bhabha Road, Pune 411008, India
§
Academy of Scientific and Innovative Research (AcSIR), New Delhi 110025, India
*
S Supporting Information
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ABSTRACT: A series of four unsymmetrical squaraine dyes, XSQ1−4, were

synthesized using a fused fluorenylindolenine-based donor unit for dye-sensitized
solar cells (DSSCs). The fused structure of fluorenylindolenine helped in moving
the absorption toward the near-infrared (NIR) region, and the two sp3-C centers
available on this donor were utilized to incorporate out-of-plane alkyl chains in
opposite directions to control the dye−dye interactions on the TiO2 surface.
High extinction coefficient (ε ≥ 105 M−1 cm−1) for absorbing NIR photons and
suitable highest occupied molecular orbital and lowest unoccupied molecular
orbital energy levels with respect to the conduction band of TiO2 and electrolyte
for charge injection and dye regeneration processes, respectively, make these dyes
potential sensitizers for DSSCs. Introduction of branched alkyl groups in the π-
framework helped in controlling dye aggregation to reduce exciton quenching and
assisted in TiO2 surface passivation to avoid the charge recombination process.
Furthermore, having a naphthyl group on the indole part of the anchoring group
containing segment helped to red-shift the absorption spectrum of dyes 15 nm toward the NIR region (XSQ3−4). Among all of
the dyes under investigation, XSQ2 gave the best photovoltaic performance, having a short-circuit current density (JSC) of 13.99
mA cm−2, open-circuit voltage (VOC) of 0.66 V, and a fill factor (ff) of 0.71, with a device performance (η) of 6.57%.
Electrochemical impedance spectroscopy revealed higher electron lifetime on TiO2 for XSQ2, which helps to avoid the charge
recombination process.
KEYWORDS: squaraine dyes, fluorenylindolenine, NIR absorption, H- and J-type aggregation, out-of-plane alkyl groups,
dye-sensitized solar cells

■ INTRODUCTION
Dye-sensitized solar cells (DSSCs) have shown potential as a
photovoltaic technology for future demand of clean and
renewable energy because of being cheaper and easy to fabricate
compared with silicon solar cells.1 The working principle of
DSSCs involves (i) a light-harvesting sensitizer, which promotes
an electron to the excited state upon absorption of light, (ii) a
metal-oxide-based semiconductor, which accepts the excited
electron and transfers it to the external circuit, (iii) an electrolyte
that regenerates the oxidized dye, and (iv) the oxidized
electrolyte collects the electron from the external circuit at the
counter electrode.2 The extensive research during the last two
and a half decades on DSSCs helped to understand charge
transport and recombination processes occurring at various
interfaces that provided guidelines to design anode materials,
sensitizers, electrolytes, and counter electrodes of the device for
the improved performance.1,3 The light-harvesting sensitizer
plays an important role in the conversion efficiency of the
DSSCs, and efforts have been devoted to developing metal-
based and metal-free efficient sensitizers. For efficient
sensitizers, it is desirable to have a broad absorption with a
high extinction coefficient (ε). The sensitizers based on
ruthenium−polypyridyl complexes remained the champion
sensitizers for almost a decade, and efficiency up to 11.8% was
achieved.4 The highest efficiency of 13% for organometallic dyes
was reported for zinc-porphyrin-based dye SM315 where the
donor−π−acceptor (D−π−A) configuration was used, with
benzothiadiazole as an acceptor, to enhance the performance of
the DSSC.5 Although these metal complexes showed broad
spectral coverage and high efficiency, low absorptivity at near-
infrared (NIR) wavelengths and difficulty in synthesis have led
the attention toward metal-free sensitizers as alternatives.
Several D−π−A type of metal-free sensitizers have also been
explored and proved to be highly efficient in terms of
performance and ease of synthesis.6 In these dyes, electron-
rich moieties like triphenylamine derivatives are used as donors
Received: June 13, 2018
Accepted: July 17, 2018
Published: July 17, 2018

© 2018 American Chemical Society 26335 DOI: 10.1021/acsami.8b09866

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Figure 1. (a) Design of steric- and electronic-effect-incorporated unsymmetrical squaraine dyes, (b) design of a fused fluorenylindolenine-based
donor, and (c) design of unsymmetrical squaraine dyes XSQ1−4.
and electron-withdrawing groups like cyanoacetic acid are used
as acceptors. They show high molar extinction coefficients due
to facile intramolecular charge transfer (ICT), which occurs
within the molecule because of the push−pull structure.7,8 Such
a structure provides the advantage of easy tweaking and
modification of the electronic nature of the π-bridge.
Furthermore, the D−A−π−A configuration helped to synthe-
size low-band-gap dyes to extend the absorption in the visible
and far-red region of the solar spectrum.9 Such a configuration
used additional acceptors like benzthiadiazole,10,11 diketopyrro-
lopyrrole,12,13 benzotriazole,14,15 benzoxadiazole,16,17 quinoxa-
line,18,19 etc. between the conventional donor and the π-bridge.
The efficiency of ≥10% was obtained with a diketopyrrolo-
pyrrole-based dye employing the [Co(bpy)3]3+/2+ electrolyte.20
Among the metal-free dyes, ≈14% device performance has been
achieved by D−π−A dyes through the cosensitization
approach.21
In DSSCs, near-infrared-absorbing organic dyes are critically
needed as they are capable of generating high current density,
which can improve the performance of the cell.22,23 Although
several sensitizers have been developed with broad absorption,
there are limited chromophores that absorb in the NIR regions
such as phthalocyanines,24 porphyrins,25−29 and polymethine30
dyes. Squaraine dyes, a subclass of polymethine dyes, are among
the few chromophores having the potential to absorb in this
region.31 Indole-based squaraine dyes are one of the most
common designs of efficient squaraine dyes where the indole
moiety is condensed with squaric acid.32 Unsymmetrical
squaraine dyes typically perform better than symmetrical ones
as the unidirectional electron flow proved to be beneficial for
better electron injection to TiO2. The first unsymmetrical
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squaraine dye showed an efficiency of 4.5% (VOC = 0.603 V and
JSC = 10.5 mA cm−2) because the asymmetric structure led to an
efficient unidirectional charge injection to TiO2.33 Although
squaraine dyes show very good absorption in the far-red region,
the exciton quenching by aggregation limits its overall
photovoltaic performance in DSSCs.34,35 The π−π interaction
between the molecules leads to aggregation of dyes on TiO2,
which is a common phenomenon and has a variable effect on the
performance of DSSCs.36−39 The periodic availability of the 5-
coordinated Ti site on the anatase {101} facet provides dye-
anchoring sites with close proximity. Such a monolayer of dyes
on the TiO2 surface allows the molecular dipoles to interact in a
head-to-head (H−H) fashion, which causes H-type aggregates
and can be observed as blue-shifted absorption in the UV−vis
spectrum with respect to the monomer, whereas the head-to-tail
(H−T) interaction leads to a J-type aggregate, which shows red-
shifted absorption.39−42 Several attempts have been made to
improve the efficiency of squaraine dyes by increasing the
absorption in the NIR region. The fused π-extended heterocyclic
structures such as benz[e]indole,43−45 benzo[c,d]indole,46,47
and quinoline48−50 have been used as strong donors in place of
indole to shift the absorption to NIR through strong ICT. These
structures could not convert the increased NIR absorption into
better performance due to either aggregation or mismatched
highest occupied molecular orbital (HOMO)−lowest unoccu-
pied molecular orbital (LUMO) levels. In another approach,
conjugation is increased by attaching a π-spacer to squaraine dye
to increase the length of the molecule, which increased the
absorption toward a longer wavelength.51−55 Remarkably, an
improved efficiency of 7.3% was obtained with the incorporation
of cyclopentadithiophene as a π-spacer in squaraine dye, which
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Scheme 1. (a) Synthesis of Fluorenylindolium Salts 6a and 6b, (b) Semisquaric Acid 8, (c) Semisquaric Acid 12, and (d)
Unsymmetrical Squaraine Dyes (XSQ1−4)

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Figure 2. (a) Absorption profile of XSQ dyes in CH2Cl2 solvent, (b) normalized fluorescence spectra excited at 600 nm, (c) absorption spectra on
TiO2, and (d) light-harvesting efficiency (LHE) of the XSQ dyes.
utilized out-of-plane hexyl chains to control aggregation as well
as enhance the absorption in the NIR region through extended
conjugation.54
The results indicate that both electronic and steric factors are
important in dye design, and certain modification in structural
features of the dyes may lead to the significant improvement in
cell efficiency. An unsymmetrical squaraine dye, DTS-CA, which
has a squaraine unit linked with a silolodithiophene (DTS) π-
spacer possessing out-of-plane ethylhexyl chains, exhibits an
efficiency of 8.9%.51 In our recent work, benzodithiophene
(BDT) bearing two ethylhexyl branched chains was used as a π-
spacer with squaraine dye, which produced the efficiency of
6.72% without a coadsorbent.56 Incorporation of an out-of-
plane alkyl chain on the sp3-center in the indole unit of squaraine
dyes helped to effectively control dye aggregation and charge
recombination (η = 9.1%).57 The approach of appending alkyl
groups to modulate the charge recombination process has been
used to boost the performance of porphyrin58−60 and
phthalocyanine dyes61−63 as well.
On the basis of these findings, we attempted to increase the
absorption of the squaraine dyes toward the NIR region and also
include out-of-plane branched alkyl chains to control
aggregation. To this end, we designed and synthesized a fused
donor where a fluorene moiety is fused with indolenine to give a
fluorenylindolenine donor. This donor can accommodate two
out-of-plane branched alkyl chains and one in-plane linear chain
on the nitrogen, which can help in controlling the aggregation of
dyes on TiO2 as well as extending conjugation toward NIR
(Figure 1).
A series of four dyes, XSQ1−4, were synthesized using this
donor. XSQ1 and XSQ2 contained indole units toward the
anchoring side with an N-methylated and N-hexylated
fluorenylindolenine donor, respectively. XSQ3 and XSQ4
contained a benz[e]indole unit toward the anchoring side with
an N-methylated and N-hexylated donor, respectively.
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■ RESULTS AND DISCUSSION
Synthesis and Characterization. The synthetic scheme
for dyes XSQ1−4 is represented in Scheme 1. Precursors 9,9-di-
n-octyl-2-bromofluorene64 (1), 7,65 10,45 and 465 were
synthesized following the previously reported protocols. To
attach the hydrazine functionality, precursor 1 was treated with
n-BuLi at −78 °C followed by addition of dibutylazadicarbox-
ylate to give tert-BOC-protected hydrazine derivative 2.
Compound 2 was unmasked by treatment with hydrochloric
acid to afford hydrazine derivative 3 in good yield.
The hydrazine derivative was refluxed with 4 (branched
methyl ketone) in acetic acid to give fluorenylindolenine 5 in
moderate yield, which was then heated with methyl iodide and
hexyl iodide in a sealed tube to afford the corresponding
fluorenylindolium salts 6a and 6b, respectively. The precursors
for the anchoring group containing indoline derivatives 761 and
949 were synthesized and further functionalized to afford the
required semisquaric acid derivatives 8, and 12, respectively
(Scheme 1). Semisquarate 7 was treated with 2 N HCl to
provide the required semisquaric acid 8 in quantitative yield.
The carboxybenz[e]indole 949 derivative was reacted with
methyl iodide to give N-methylated carboxybenz[e] indolium
salt 10, which was then reacted with dibutyl squarate. The
squarate intermediate was then reacted with 2 N HCl to provide
the required semisquaric acid 12. Semisquaric acid 8 was
refluxed with 6a in a n-BuOH/PhMe mixture under azeotropic
distillation of water employing a Dean−Stark apparatus to give
squaraine dyes XSQ1, whereas dye XSQ2 was obtained by
reacting 8 with 6b. Similarly, dyes XSQ3 and XSQ4 were
obtained by treating semisquaric acid 12 with 6a and 6b,
respectively. All of the dyes were completely characterized, and
their structural and electronic properties were thoroughly
investigated by NMR spectroscopic and mass spectrometric
techniques.
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Table 1. Photophysical and Electrochemical Properties of XSQ Dyes

λmax/CH2Cl2 λmax/em (nm) in λmax/TiO2 Eg/DFT EHOMO E0−0 ELUMO
dyes (nm) CH2Cl2 (nm) Amax/monomerAmax ε × 105 (M−1 cm−1)
dimer
(eV) (V vs NHE) (eV) (V vs NHE)
XSQ1 665 673 625/670 0.67 2.2 2.19 0.78 1.85 −1.09
XSQ2 666 674 628/672 0.60 3.0 2.19 0.75 1.85 −1.10
XSQ3 679 686 635/684 0.70 2.4 2.18 0.67 1.82 −1.15
XSQ4 681 687 637/686 0.69 3.5 2.17 0.66 1.81 −1.15

Figure 3. (a) Cyclic voltammogram of XSQ dyes measured in CH2Cl2 (platinum wire as the working electrode, nonaqueous Ag/Ag+ (0.01 M) as the
reference electrode, and platinum foil as the counter electrode) with TBAClO4 (0.1 M) at a scan rate of 50 mV s−1. (b) Energy-level diagram for XSQ
dyes with DSSC device components.

Photophysical Studies. The optical properties of XSQ1−4
in CH2Cl2 and on a transparent thin film of TiO2 (6 μm) are
shown in Figure 2 and summarized in Table 1. Dyes XSQ1−4
displayed intense absorption (ε ≥ 105 M−1 cm−1) toward the far-
red region in solution due to efficient ICT.
The absorption spectra mainly spanned from 545 to 698 nm
for XSQ1−2, whereas XSQ3−4 had the major absorption
between 553 and 711 nm. The absorption maxima (λmax) of
XSQ1−2 were found to be at 665 and 666 nm, whereas XSQ3−
4 showed a red shift of ca. 15 nm with λmax at 679 and 681 nm.
Compared with its parent squaraine dye SQ1 (λmax = 640 nm),57
XSQ1−2 and XSQ3−4 had 25 and 40 nm red-shifted
absorption, respectively, because of the extended conjugation
by fused fluorenylindolenine and benz[e]indole moieties. The
shoulder peaks between 600 and 640 nm were observed due to
the vibronic progression. To understand the aggregation of dyes
in solution, the concentration-dependent UV−vis study has
been carried out using quartz cuvette of 0.1 cm path length. It
was observed that dyes exist as monomers in moderate
concentrations (6.25−50 μM); however, at the higher
concentration (100 μM), the deviation in the Beer−Lambert
plot suggests the formation of aggregates in solution (Figure S1).
The absorption spectra of XSQ dyes on chemisorbed TiO2 films
were obtained by dipping a transparent, 6 μm thick, TiO2 film in
0.1 mM dye solution in EtOH for 15 min (Figure 2c). The
broadening of the spectra with coverage from 550 to 715 nm was
observed for XSQ1−2, whereas spectra covered from 550 to 730
nm for XSQ3−4. The λmax on the TiO2 film is slightly red-shifted
to about 5 nm compared to that for the solution, and there was
emergence of an additional peak also at a shorter wavelength
(620−640 nm) because of H-type aggregation on TiO2, which
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leads to dimer formation. The formation of a dimer was
confirmed by carrying out the UV−vis studies of chenodeox-
ycholic acid (CDCA)-co-adsorbed dye-sensitized TiO2 films,
where the intensity of peaks observed at 600−640 nm was
decreased because of the reduction in dimer formation
compared to that for the dye-sensitized TiO2 films without
CDCA (Figure S2). The ratio of the optical density of the
monomer to the dimer (Adimer/Amonomer) is given in Table 1, and
it helped in concluding the extent of aggregation for each dye on
the surface, which revealed that XSQ2 is the least aggregated in
comparison to other dyes. Apart from the peaks at the low-
energy region, there is a band of high-energy absorption between
400 and 550 nm with relatively low absorbance. The light-
harvesting efficiency (LHE = 1 − 10−A) represents the capacity
of sensitizers to absorb a wide range of photons on the TiO2 thin
film (Figure 2d). The LHE profile of all of the dyes indicated
over 90% light harvesting in the wide spectral range of 560−730
nm, and XSQ3−4 showed a 20 nm red-shifted onset compared
with XSQ1−2. The variable LHE response was observed in the
high-energy region of 400−550 nm where XSQ4 showed the
maximum intensity.
Electrochemical Properties. To evaluate the feasibility of
charge injection and dye regeneration process for XSQ1−4
dyes, cyclic voltammetry was carried out in a CH2Cl2 solution
with tetrabutylammonium perchlorate (TBAClO4) as the
electrolyte and ferrocene as an external reference. The cyclic
voltammograms of XSQ dyes exhibit two-electron oxidation
peaks, which is a characteristic of squaraine dyes (Figure 3a). For
efficient electron transfer from the excited dye to TiO2, the
excited-state potential (LUMO) of the dye should be more
negative than the conduction band (CB) edge (−0.5 V vs
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Figure 4. Optimized geometry structure of XSQ2 and XSQ4 and CDCA (a) lateral view and (b) top view (distance between the sp3-C atom of
fluorenyl and the oxygen atom of carboxylic acid and distance between the sp3-C atom of indoline and the oxygen atom of carboxylic acid were
provided).
Figure 5. Isodensity plots of XSQ2 and XSQ4 (alkyl chains are removed for clarity).
normal hydrogen electrode (NHE)) of TiO2 (at least 0.2 eV66),
whereas the ground-state potential (HOMO) of the dye should
be more positive than the redox potential (0.4 V vs NHE) of
iodide/triiodide (at least 0.15 eV67) to provide sufficient driving
force for efficient regeneration of the oxidized dye. The HOMO
level of XSQ dyes was calculated from the first oxidation peak
and found to be at 0.76 V (XSQ1), 0.75 V (XSQ2), 0.67 V
(XSQ3), and 0.66 V (XSQ4), which are lower than the
electrochemical potential of redox mediator (I−/I3−) to provide
enough driving force for dye regeneration (Figure 3b).
The HOMO levels of XSQ3−4 were 90 mV above those of
XSQ1−2, which could be attributed to the stronger electron-
releasing effect of the carboxybenz[e]indole unit present on the
anchoring end of XSQ3−4. The LUMO energy levels of the
dyes were calculated by subtracting E0−0 from the HOMO levels
of the dyes and found to be at −1.09 V (XSQ1), −1.10 V
(XSQ2), −1.15 V (XSQ3), and −1.15 V (XSQ4), which lie well
above the conduction band level of TiO2, hence suitable for
efficient electron injection into TiO2.
Computational Investigations. Optimized molecular
geometries and electronic distribution of frontier molecular
orbitals in XSQ dyes were computed by Gaussian 09.68 The two
opposite branched alkyl chains on the fluorenylindolenine unit
were 14.7 and 20 Å away from the anchoring carboxylic acid
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group in XSQ2 (Figure 4). In the XSQ4 dye, the branched
chains were at distances of 16 and 21 Å from the terminal atom
of the anchoring group because of the increase in the length
caused by the extended benz[e]indole unit. The top view of
these molecules showed that the alkyl chains are stretched up to
18−20 Å in the out-of-plane direction, which can help in
controlling aggregation of dyes on the TiO2 surface efficiently.
Because the dimension of the CDCA molecule (14.2 Å) is on
the order of the distance between the lower branched chain and
anchoring groups of XSQ1 and XSQ2 (14.7 Å), the adsorption
of CDCA may affect the dye loading. However, in the case of
XSQ3 and XSQ4, the distance between the lower branched
chain and the anchoring group unit is larger than the dimensions
of the CDCA molecule and the CDCA molecules can occupy
the space under the dye molecules when co-adsorbed on TiO2,
which may help in passivating the TiO2 surface more effectively.
Furthermore, the additional N-alkyl group also increases the
density of the alkyl group around the lower branching unit of
dyes XSQ2 and XSQ4, which decreases the amount of dye
loaded on the surface compared to that in XSQ1 and XSQ3. The
electron density distribution in the frontier molecular orbitals
(HOMO and LUMO) of the dyes under investigation is shown
by isodensity plots in Figure 5. The electron density in HOMO
of both indole (XSQ1 and XSQ2) and benzindole (XSQ3 and
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Figure 6. (a) J−V curve and (b) IPCE spectrum of XSQ1−4-sensitized cells with 3 equiv of CDCA (TiO2 electrode thickness = 8 + 4 μm (transparent
+ scattering layer), area = 0.36 cm2, [dye] = 0.1 mM in EtOH, [CDCA] = 0.3 mM, dipping time = 12 h at room temperature (rt), electrolyte: iodolyte
Z-50, mask aperture 0.64 cm2 from Solaronix).

Figure 7. (a) J−V curve and (b) IPCE spectrum of XSQ2-sensitized dyes with varying CDCA concentrations in the dye solution in EtOH (TiO2
electrode thickness = 8 + 4 μm (transparent + scattering layer), area = 0.36 cm2, [dye] = 0.1 mM in EtOH, dipping time = 12 h at rt, electrolyte:
iodolyte Z-50, mask aperture 0.64 cm2 from Solaronix).

Table 2. Photovoltaic Performance of XSQ Dyes with and without CDCA under 1 sun Illumination and the Results of Five
Devices for Each Set with Deviation Are Summarized
dye VOC (V) JSC (mA cm−2) INT
JSC (mA cm−2)a ff (%) η (%) dye loading (mol cm−2)
XSQ1 0.621 ± 0.003 7.2 ± 0.11 6.55 70.1 ± 0.13 3.21 ± 0.13 8.68 × 10−8
XSQ1/CDCA (1:3) 0.652 ± 0.003 12.6 ± 0.13 11.85 70.0 ± 0.4 5.75 ± 0.15 8.06 × 10−8
XSQ2 0.634 ± 0.002 9.21 ± 0.2 8.82 71.1 ± 0.2 4.12 ± 0.12 7.81 × 10−8
XSQ2/CDCA (1:3) 0.657 ± 0.002 13.8 ±0.19 13.57 71.2 ± 0.3 6.42 ± 0.15 7.11 × 10−8
XSQ3 0.616 ± 0.002 5.3 ± 0.21 5.23 69.1 ± 0.13 2.25 ± 0.11 1.36 × 10−7
XSQ3/CDCA (1:3) 0.643 ± 0.002 8.98 ± 0.2 8.5 70.2 ± 0.2 4.05 ± 0.14 1.10 × 10−7
XSQ4 0.591 ± 0.002 8.3 ± 0.21 8.11 68.9 ± 0.4 3.38 ± 0.16 6.27 × 10−8
XSQ4/CDCA (1:3) 0.633 ± 0.002 12.1 ± 0.18 11.77 70.1 ± 0.4 5.37 ± 0.13 6.22 × 10−8
a
Calculated by integrating IPCE over the corresponding wavelengths.

XSQ4) dyes is located mostly in the central squaraine unit with a
slight spread in the fluorenylindolenine unit. In the LUMO
energy level, there is a clear shift of the electron density from the
fluorenylindolenine unit toward the anchoring group for both
the dyes, which is significant for the facile charge transfer. It also
ensures the good electronic coupling between the excited-state
dye and TiO2 because of the presence of sufficient electron
density on the anchoring group, which is important for the
efficient injection of electrons from the excited dye molecule
into the conduction band of TiO2. However, the bent structure
of XSQ3−4 due to the benz[e]indole group may lead to
nondirectionality in the molecular dipole, which can be observed
by comparing the calculated dipole moments of XSQ1 (10.0 D)
and XSQ2 (10.6 D) with XSQ2 (7.4 D) and XSQ4 (7.3 D)
(Figure S7). The resultant dipole moment exerted by the dye
molecules on the TiO2 surface plays a vital role in modulating
the conduction band energy level and hence the VOC.69,70
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Photovoltaic Performance. Current−voltage (J−V) char-
acteristics and the incident photon-to-current conversion
efficiency (IPCE) profiles are displayed in Figures 6 and 7,
and photovoltaic data are summarized in Table 2. All of the dyes
gave moderate DSSC performance in the absence of any
coadsorbent with the XSQ2 dye, exhibiting the maximum power
conversion efficiency (PCE) of 4.12% with JSC of 9.22 mA cm−2
and VOC of 0.636 V, whereas XSQ3 showed the minimum
efficiency of 2.36% with JSC of 5.51 mA cm−2, VOC of 0.618 V,
and fill factor (ff) of 69.23%. XSQ1 and XSQ4 showed the
efficiency of 3.34 and 3.54%, respectively. Although the VOC of
these cells varies slightly, the significant variation in the
efficiencies of the dyes comes from the difference in their JSC.
The gradual increase in the amount of coadsorbent (CDCA)
improved the performance of the cells, and all of the XSQ dyes
gave their best photovoltaic properties at 3 equiv of CDCA.
XSQ2 showed the highest efficiency among all of the dyes with
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Figure 8. Impedance analysis of XSQ1−4 DSSC devices. (a) Nyquist plot at an applied bias of −0.5 V (inset: equivalent circuit), (b) log Rct vs applied
potential, (c) log Cμ vs applied potential, and (d) τ vs applied potential.
PCE of 6.57% mostly due to 50% increment in JSC (13.99 mA
cm−2) and 5% incremental improvement in VOC (0.657 V) after
addition of 3 equiv of the CDCA. The addition of CDCA helps
avoiding the dye−dye interaction (dye aggregation) and
passivates the TiO2 surface so that the oxidized electrolyte
may not diffuse through the hydrophobic layer to reach the
surface of TiO2 that avoids the charge recombination, which
resulted in an increase in JSC and VOC. The trends in JSC can be
correlated to IPCE spectra of the cells (Figure 6b).
The IPCE spectra of the XSQ dyes showed a good response in
the region of 500−750 nm with XSQ2 having the best profile
with 76% IPCE at 620 and ca. 40% IPCE between 400 and 500
nm. XSQ1 and XSQ4 displayed similar IPCE trace, result of
which could be observed in their similar JSC values of 12.73 and
12.28 mA cm−2, respectively. XSQ3 has the poorest response
managing up to only 40% IPCE between 600 and 720 nm and
around 22% between 400 and 550 nm. It was observed that by
increasing the concentration of CDCA up to 3 equiv, JSC values
were increased significantly without affecting the distribution of
IPCE response from the aggregated state. This indicated that the
formation of larger aggregates was decreased and the smaller
aggregates could effectively participate in the charge injection
process. Apart from substantial increase in JSC, the modest
increase in VOC was also obtained upon addition of CDCA
because of improved charge injection and reduced charge
recombination. A moderate decrease in VOC and JSC upon
further increasing the CDCA concentration indicated depletion
of the amount of dye on the TiO2 surface. It is interesting to note
that the decrease in the amount of adsorbed dyes in the presence
of 3 equiv of CDCA is very low, ca. 8−19%, whereas the increase
in short-circuit current density is significantly high, 44−74%. For
example, in the case of XSQ2, the decrease in dye loading is only
8.9% after addition of 3 equiv. of CDCA, whereas the increase in
JSC is ca. 36%. Similarly, XSQ1 observed 74% increase in JSC in
the presence of 3 equiv of CDCA, which shows that CDCA is
able to control aggregation without replacing the dye (Figures 6
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and 7a,b). These observations can be explained if we take into
account the possibility that instead of replacing the dye CDCA is
taking up the void spaces between the dyes. It is also supported
by the density functional theory (DFT) calculations which show
that the branched alkyl chains are stretching up to 20 Å in the
out-of-plane direction, which may create enough gap for the
CDCA molecule to anchor between dyes, and also the distance
between the lower branch chain and the terminal oxygen atom of
carboxylic acid (14.7 and 16 Å for XSQ2 and XSQ4,
respectively) is greater than the length of CDCA (14.2 Å).
Hence, it is conceivable that the CDCA molecule might anchor
just between the dyes and the dye amount essentially remains
the same. Such preferential self-assembled monolayers of dyes
act as a hydrophobic barrier layer because of the presence of out-
of-plane alkyl groups at sp3-C atoms and alkyl chains at the N-
atom, which avoids the charge recombination of electrons from
TiO2 to the oxidized electrolyte. It is also noted that dyes with N-
hexyl alkyl chains showed better efficiency than N-methylated
dyes as XSQ1 showed the η of 5.90%, which is lower in
comparison to that of XSQ2. A similar trend was observed for
the benz[e]indole-based dye where XSQ3 showed η of 4.19%,
which is lower than the efficiency of the XSQ4 (η = 5.5%)-based
cell. This observation suggests that the N-hexyl chain could help
the dyes assemble favorably on to the TiO2 surfaces besides
passivating the surface. Additionally, the VOC values of indole-
based XSQ1−2 are slightly higher than those of XSQ3−4
(ΔVOC ≈ 10 mV), which can be attributed to the upshift in the
conduction band (CB) edge due to greater dipole moments of
XSQ1−2 in the direction normal to TiO2.69,70
Electrochemical Impedance Spectroscopy (EIS). To
understand the charge transfer and recombination processes at
the various interfaces of a DSSC device, EIS study was carried
out in the dark at various applied potentials, viz., 0.38, 0.41, 0.47,
and 0.50 V.
As the device architecture and electrolytes, including
fabrication conditions, are similar for all of the cells, any
DOI: 10.1021/acsami.8b09866
ACS Appl. Mater. Interfaces 2018, 10, 26335−26347
ACS Applied Materials & Interfaces
characteristic feature obtained in EIS is mainly due to the
interaction of dyes at the TiO2−dye/electrolyte interface. The
Nyquist plots at an applied bias of 0.50 V are shown in Figure 8a.
The larger semicircle in the intermediate frequency region gives
the information regarding charge transfer dynamics at the dye-
sensitized TiO2−electrolyte interface, and the radius of the
semicircle gives the recombination resistance (Rct).
The Rct values of XSQ-sensitized cells do not vary
significantly, and they have the approximately same Rct value
at −0.50 V applied bias, which could be expected as all of the
dyes have similar crowded branched chains, resulting in equal
surface passivation to TiO2. The trend in chemical capacitance
(Cμ) is slightly different, and XSQ1−2 have a higher Cμ
compared to that of XSQ3−4, which ultimately results in the
longer lifetime (τ = Rct × Cμ) for XSQ1−2 dyes than for XSQ2−
4. Generally, the electron lifetime on TiO2 affects the VOC of
DSSC and the τ values of XSQ-dye-based cells (without CDCA)
follow the same trend as VOC, i.e., XSQ3 (9.8 ms) < XSQ4 (10.0
ms) < XSQ1 (13.9 ms) < XSQ2 (14.6 ms) (Table 3). Dyes
Table 3. EIS Parameters of XSQ Dye Cells at −0.5 V
XSQ dyes Rs (Ω) Rct (Ω) Cμ (mF) τ (ms)
XSQ1 13.6 6.3 2.2 13.9
XSQ2 13.9 6.1 2.4 14.6
XSQ3 12.4 6.1 1.6 9.8
XSQ4 13.1 5.9 1.7 10.0
XSQ1 and XSQ2 have higher dipole moments, which may bring
the conduction band slightly upward, allowing a higher
concentration of electrons on TiO2 in comparison with XSQ2
and XSQ4 dyes, which leads to a greater electron lifetime in
XSQ1−2-based DSSCs.69,70
■
CONCLUSIONS
The electronic and steric factors of the dyes play a significant
role in determining the device performance of DSSCs. A series
of XSQ dyes were synthesized with a fused fluorenylindolenine-
based donor that not only helps in increasing conjugation but
also allows appending out-of-plane alkyl chains through sp3-C
atoms to avoid aggregation. All of the dyes showed good
absorption in the NIR spectral region, with the absorption of
benz[e]indole-based dyes XSQ3−4 more red-shifted than that
of indole-based XSQ1−2. Owing to extensive coverage of
branched out-of-plane alkyl chains on both sides of the
molecular plane, aggregation was effectively controlled in all of
the dyes. DFT-based calculations predicted efficient electron
transfer toward TiO2 and show higher dipole moments for
XSQ1−2 in comparison to those for XSQ3−4. XSQ2 showed
the best photovoltaic performance with the PCE of 6.57% in the
presence of 3 equivalents of CDCA due to the higher short-
circuit current density, and EIS analysis indicated a higher
electron lifetime on TiO2 for XSQ2-sensitized solar cell, which
explains its slightly greater VOC.
■
EXPERIMENTAL SECTION
Precursors 1,64 8,61 and 1045 were synthesized by following a literature
procedure. Details on the reagents, equipment utilized to characterize
the synthesized precursors, final dye molecules, further evaluation of the
photophysical, electrochemical, and photovoltaic parameters and
electrochemical impedance spectroscopy were provided in the
Supporting Information. The procedures for the DSSC device
fabrication with the mask (active area of the cell 0.36 cm2 and mask
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Research Article
aperture 0.64 cm2) and without the mask (active area 0.22 cm2) have
been provided in the Supporting Information.
Synthetic Procedure. Di-tert-butyl 1-(9,9-dioctyl-9H-fluoren-2-
yl)hydrazine-1,2-dicarboxylate (2). n-BuLi (1.6 M, 4.8 mL, 7.7 mmol)
was added slowly to a stirred solution of 9,9-di-n-octyl-2-bromo-
fluorene, 164 (3.0 g, 6.4 mmol), in anhydrous tetrahydrofuran (THF, 35
mL) at −78 °C, under a nitrogen atmosphere. After stirring for 30 min,
di-tert-butylazodicarboxylate (3.2 g, 14.1 mmol) dissolved in anhydrous
THF (35 mL) was added to the reaction mixture. After stirring at −78
°C for 2 h, the mixture was allowed to warm to rt and stirred for 18 h.
Glacial acetic acid (1.5 mL) was added slowly, and the mixture was
stirred for a further 4 h at rt. Et2O (50 mL) and water (50 mL) were
added. The aqueous layer was separated and extracted with ether (2 ×
60 mL). The combined organic extracts were then washed with brine
(60 mL), dried over Na2SO4, filtered, and concentrated. The crude
material was purified by column chromatography on silica (SiO2,
CH2Cl2/petroleum ether as eluents) to give 2 as sticky gum (2.72 g,
68%). 1H NMR (200 MHz, CDCl3) δ: 7.72−7.53 (m, 2H), 7.42−7.25
(m, 5H), 1.93 (t, J = 8.0 Hz, 4H), 1.50 (s, 18H), 1.08 (d, J = 19.7 Hz,
20H), 0.81 (t, J = 6.7 Hz, H), 0.73−0.47 (m, 4H); 13C NMR (100 MHz,
CDCl3) δ: 155.7, 154.0, 153.9, 151.0, 141.6, 140.7, 138.9, 126.9, 126.9,
122.9, 119.7, 119.6, 82.2, 81.6, 55.2, 40.5, 31.9, 30.2, 29.4, 28.3, 23.9,
22.7, 14.2; high-resolution mass spectrometry (HRMS) (ESI) m/z: [M
+ H]+ calcd for C39H61O4N2: 621.4626; found: 621.4628.
2-(9,9-Dioctyl-9H-fluoren-2-yl)hydrazin-1-ium Chloride (3). A
solution of concentrated hydrochloric acid (4.1 mL) in 1,4-dioxane
(12 mL) was added to a solution of 2 (2.8 g, 4.5 mmol) in 2-propanol
(25 mL). The reaction mixture was heated at 85 °C for 1 h. After
cooling to room temperature, the solvent was completely removed to
give 3 as pink sticky gum (1.85 g, 90%), which was used directly in the
next step without purification.
3-Decyl-2-methyl-3,9,9-trioctyl-3,9-dihydroindeno[1,2-f ]indole
(5). Compound 3 (1.5 g, 3.3 mmol) and 3-octyltridecan-2-one, 465 (2.0
g, 6.6 mmol), were taken with 30 mL of acetic acid in a round-bottomed
flask. The resultant mixture was heated for 3 days at 90 °C. After the
completion of the reaction, the solvents were removed under reduced
pressure. The residue was dissolved in CH2Cl2 and washed with 5%
KOH solution. The organic layer was collected, dried over Na2SO4, and
purified by column chromatography (SiO2, CH2Cl2/petroleum ether)
to afford 5 as dark yellow oil (0.570 g, 25%). 1H NMR (200 MHz,
CDCl3) δ: 7.68 (d, J = 7.6 Hz, 1H), 7.47 (s, 1H), 7.45 (s, 1H), 7.38−
7.27 (m, 3H), 2.23 (s, 3H), 2.03−1.92 (m, 4H), 1.75 (d, J = 35.2 Hz,
4H), 1.13 (dd, J = 30.5 Hz, 17.4 Hz, 46H), 0.80 (t, J = 6.6 Hz, 12H),
0.61 (s, 6H); 13C NMR (100 MHz, CDCl3) δ: 186.6, 155.2, 151.3,
151.0, 141.6, 141.4, 138.4, 126.7, 126.6, 122.9, 119.3, 114.3, 112.9, 62.5,
55., 40.7, 37.4, 32.0, 31.9, 30.2, 30.0, 29.9, 29.7, 29.6, 29.4, 29.4, 29.3,
23.9, 23.8, 22.8, 22.7, 16.4, 14.2; matrix-assisted laser desorption
ionization time-of-flight m/z: [M + H]+ calcd for C50H82N: 696.6447;
found: 696.4977.
3-Decyl-1,2-dimethyl-3,9,9-trioctyl-3,9-dihydroindeno[1,2-f ]-
indol-1-ium Iodide (6a). A mixture of 5 (0.15 g, 0.22 mmol) and MeI
(0.125 g, 0.86 mmol) in MeCN (5 mL) was heated under a N2
atmosphere at 85 °C for 24 h in a sealed pressure tube. The reaction
mixture was cooled to rt before the solvent and excess MeI were
completely removed under vacuum to give compound 6a (70%, 0.13 g),
which was used further without purification.
3-Decyl-1-hexyl-2-methyl-3,9,9-trioctyl-3,9-dihydroindeno[1,2-
f ]indol-1-ium Iodide (6b). A mixture of 5 (0.15 mg, 0.22 mmol) and 1-
iodohexane (0.183 g, 0.86 mmol) in MeCN (5 mL) was heated under
nitrogen at 85 °C for 24 h in a sealed pressure tube. The reaction
mixture was cooled to room temperature before the solvent and excess
1-iodohexane were completely removed in vacuo to give compound 6b
(65%, 0.130 g), which was used further without purification.
(E)-2-((2-Hydroxy-3,4-dioxocyclobut-1-en-1-yl)methylene)-1,3,3-
trimethylindoline-5-carboxylic Acid (8). In a 50 mL round-bottomed
flask, 7 (0.37 g, 1 mmol) was dissolved in acetone (15 mL). HCl (2 N, 2
mL) was added to the mixture and refluxed for 8 h. The solvent was
removed under reduced pressure to afford product 8, which was used
without any further purification (0.28 g, 89%). 1H NMR (500 MHz,
dimethyl sulfoxide (DMSO)-d6) δ: 7.81−7.93 (m, 2H), 7.16 (d, J =
DOI: 10.1021/acsami.8b09866
ACS Appl. Mater. Interfaces 2018, 10, 26335−26347
ACS Applied Materials & Interfaces
8.77 Hz, 1H), 5.53 (s, 1H), 3.36 (s, 3H), 1.57 (s, 6H); 13C NMR (100
MHz, DMSO-d6) δ: 193.2, 192.6, 174.0, 167.3, 165.4, 147.3, 140.1,
130.3, 123.6, 122.8, 107.9, 83.5, 46.3, 29.8, 26.7; HRMS (ESI) m/z: [M
+ H]+ calcd for C17H16NO5: 314.1023; found: 314.1012.
7-Carboxy-1,1,2,3-tetramethyl-1H-benzo[e]indol-3-ium Iodide
(10). Compound 945 (1 g, 3.95 mmol), MeI (2.8 g, 19.75 mmol),
and MeCN (8 mL) were taken in a sealed tube and heated at 150 °C for
48 h. After the completion of the reaction, the contents were poured
into 50 mL of Et2O and the precipitate obtained was filtered. The
residue was washed with diethyl ether (3 × 20 mL) and dried under
vacuum to give compound 10 (0.78 g, 50%). 1H NMR (200 MHz,
DMSO-d6) δ: 8.87 (s, 1H), 8.52 (d, J = 6.3 Hz, 1H), 8.47 (d, J = 6.1 Hz,
1H), 8.26−8.13 (m, 2H), 4.11 (s, 3H), 2.90 (s, 3H), 1.76 (s, 6H); 13C
NMR (100 MHz, DMSO-d6) δ: 197.3, 167.1, 141.3, 136.5, 132.4,
132.3, 132.2, 129.1, 129.0, 127.5, 124.0, 114.9, 55.5, 35.3, 21.3, 14.2;
HRMS (ESI) m/z: [M]+ calcd for C17H18NO2+: 268.1332; found:
268.1325.
(E)-2-((2-Butoxy-3,4-dioxocyclobut-1-en-1-yl)methylene)-1,1,3-
trimethyl-2,3-dihydro-1H-benzo[e]indole-7-carboxylic Acid (11). To
a mixture of 10 (0.5 g, 1.26 mmol) in 20 mL of n-BuOH, 3,4-
dibutoxycyclobut-3-ene-1,2-dione (0.72 g, 3.16 mmol) was added. To
the stirring mixture, NEt3 (0.38 g, 3.78 mmol) was added dropwise. The
resultant mixture was stirred at room temperature for 12 h followed by
heating at 70 °C for 3 h. Solvents were evaporated after the completion
of reaction, and the crude product was purified by column
chromatography (SiO2, MeOH/CH2Cl2) to afford 11 (0.37 g, 70%).
1
H NMR (200 MHz, DMSO-d6) δ: 8.63 (s, 1H), 8.23 (d, J = 9.1 Hz,
1H), 8.17 (d, J = 9.1 Hz, 1H), 8.00 (dd, J = 8.9 Hz, 1.6 Hz, 1H), 7.69 (d,
J = 8.9 Hz, 1H), 5.39 (s, 1H), 4.82 (t, J = 6.6 Hz, 2H), 3.52 (s, 3H),
1.95−1.70 (m, 8H), 1.46 (dq, J = 14.4, 7.2 Hz, 2H), 0.96 (t, J = 7.3 Hz,
3H); 13C NMR (125 MHz, DMSO-d6) δ: 192.3, 188.1, 186.9, 172.1,
170.0, 167.4, 142.6, 132.5, 131.5, 131.3, 129.8, 129.4, 126.6, 125.3,
122.3, 111.7, 81.4, 73.6, 48.9, 31.6, 30.3, 26.2, 18.2, 13.6; HRMS (ESI)
m/z: [M + H]+ calcd for C25H26O5N: 420.1805; found: 420.1794.
(E)-2-((2-Hydroxy-3,4-dioxocyclobut-1-en-1-yl)methylene)-1,1,3-
trimethyl-2,3-dihydro-1H-benzo[e]indole-7-carboxylic Acid (12). To
a solution of 11 (0.35 g, 0.834 mmol) in 10 mL of acetone, 1 mL of 2 N
HCl was added. The resultant mixture was refluxed for 8 h, and solvents
were removed under reduced pressure after the completion of reaction.
The crude compound 12 (0.286 g, 94%) was used further without
purification. 1H NMR (200 MHz, DMSO-d6) δ: 8.60 (s, 1H), 8.21 (d, J
= 8.8 Hz, 1H), 8.12 (d, J = 8.9 Hz, 1H), 7.97 (d, J = 8.5 Hz, 1H), 7.62 (d,
J = 8.8 Hz, 1H), 5.56 (s, 1H), 3.47 (s, 3H), 1.83 (s, 6H); 13C NMR (100
MHz, DMSO-d6) δ: 192.7, 192.1, 191.6, 173.6, 167.7, 167.4, 142.9,
132.5, 131.3, 130.7, 129.9, 129.0, 126.4, 124.9, 122.1, 111.4, 82.3, 48.4,
30.0, 26.3; HRMS (ESI) m/z: [M + H]+ calcd for C21H18O5N:
364.1179; found: 364.1170.
General Procedure for the Synthesis of Unsymmetrical
Squaraine Dyes, XSQ1−4. 6a or 6b (1 equiv) and semisquaric acid
derivatives 8 or 12 (2 equiv) were taken in a 100 mL round-bottomed
flask fitted with a Dean−Stark apparatus. n-BuOH/PhMe (20 mL, 1:1)
was added, and the contents were refluxed for 24 h. After completion of
reaction, solvents were removed under reduced pressure and the
residue was purified by column chromatography (MeOH/CH2Cl2) to
give pure compound XSQ dyes. For the synthesis of XSQ3−4, 2 mL of
DMSO was added along with 20 mL of n-BuOH/PhMe (1:1).
(E)-2-(((E)-5-Carboxy-1,3,3-trimethylindolin-2-ylidene)methyl)-4-
((3-decyl-1-methyl-3,9,9-trioctyl-3,9-dihydroindeno[1,2-f ]indol-1-
ium-2-yl)methylene)-3-oxocyclobut-1-en-1-olate (XSQ1). Started
with 6a (0.2 g, 0.24 mmol) and 8 (0.156 g, 0.48 mmol). Yield: 0.165
g, 68%. 1H NMR (500 MHz, CDCl3) δ: 8.12 (d, J = 8.3 Hz, 1H), 8.06
(s, 1H), 7.73 (d, J = 7.4 Hz, 1H), 7.58 (s, 1H), 7.38−7.28 (m, 3H),
7.03−6.92 (m, 2H), 6.18 (s, 1H), 5.99 (s, 1H), 3.71 (s, 3H), 3.52 (s,
3H), 2.09−2.00 (m, 4H), 1.98−1.92 (m, 2H), 1.85 (s, 6H), 1.21−1.16
(m, 6H), 1.14−1.01 (m, 40H), 0.83−0.74 (m, 14H), 0.63−0.51 (m,
6H); 13C NMR (125 MHz, CDCl3) δ: 182.1, 170.6, 151.9, 150.7, 147.7,
144.1, 142.0, 140.6, 139.1, 138.8, 131.3, 127.1, 124.1, 123.0, 119.7,
113.8, 108.0, 88.3, 59.3, 55.4, 48.2, 40.7, 32.0, 31.9, 30.6, 30.1, 29.7,
29.6, 29.39, 29.35, 29.3, 29.2, 27.5, 24.2, 23.8, 22.7, 22.7, 14.2; HRMS
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(ESI) m/z: [M + H]+ calcd for C68H97N2O4: 1005.7448; found:
1005.7446.
(E)-2-(((E)-5-Carboxy-1,3,3-trimethylindolin-2-ylidene)methyl)-4-
((3-decyl-1-hexyl-3,9,9-trioctyl-3,9-dihydroindeno[1,2-f ]indol-1-
ium-2-yl)methylene)-3-oxocyclobut-1-en-1-olate (XSQ2). Started
with 6b (0.2 g, 0.22 mmol) and 8 (0.104 g, 0.330 mmol). Yield: 0.15
g, 60%. 1H NMR (500 MHz, CDCl3) δ: 8.13 (d, J = 8.4 Hz, 1H), 8.07
(s, 1H), 7.73 (d, J = 7.4 Hz, 1H), 7.59 (s, 1H), 7.34 (td, J = 14.5, 7.1 Hz,
3H), 6.96 (d, J = 7.7 Hz, 2H), 6.22 (s, 1H), 6.00 (s, 1H), 4.19 (s, 2H),
3.52 (s, 3H), 3.11 (s, 2H), 2.04 (dd, J = 17.7 Hz, 9.7 Hz, 4H), 1.99−
1.91 (m, 2H), 1.86 (s, 6H), 1.47−1.38 (m, 2H), 1.35−1.24 (m, 6H),
1.20−1.15 (m, 6H), 1.12−1.01 (m, 37H), 0.86 (t, J = 7.0 Hz, 3H),
0.83−0.74 (m, 15H), 0.70−0.45 (m, 8H); 13C NMR (125 MHz,
CDCl3) δ: 181.8, 175.3,171.3, 170.7, 168.10, 151.6, 150.76, 147.78,
143.8, 147.7, 143.8, 141.9, 140.6, 139.4, 138.7, 131.3, 127.1, 124.1,
124.1 122.9, 119.67, 114.2, 113.87, 108.0, 104.7, 88.2, 59.32, 59.2, 55.3,
48.2, 40.7, 40.4, 32.0, 31.93, 31.90, 31.78, 31.7, 30.5, 30.1, 29.7, 29.6,
29.4, 29.3, 29.2, 27.8, 27.5, 27.1, 24.2, 23.9, 22.7, 22.67, 22.65, 14.2,
14.1; HRMS (ESI) m/z: [M + H]+ calcd for C73H107N2O4: 1075.8231;
found: 1075.8220.
(E)-2-((E)-(7-Carboxy-1,1,3-trimethyl-1,3-dihydro-2H-benzo[e]-
indol-2-ylidene)methyl)-4-((3-decyl-1-methyl-3,9,9-trioctyl-3,9-
dihydroindeno[1,2-f ]indol-1-ium-2-yl)methylene)-3-oxocyclobut-
1-en-1-olate (XSQ3). Started with 6a (0.180 g, 0.22 mmol) and 12
(0.156 g, 0.43 mmol). Yield: 0.11 g, 48%. 1H NMR (500 MHz, CDCl3)
δ: 8.74 (s, 1H), 8.36−8.12 (m, 2H), 7.99 (s, 1H), 7.72 (d, J = 7.3 Hz,
1H), 7.57 (s, 1H), 7.39−7.27 (m, 4H), 6.95 (s, 1H), 6.19 (s, 1H), 6.05
(s, 1H), 3.64 (s, 5H), 3.11 (s, 1H), 2.22−2.06 (m, 6H), 2.06−1.89 (m,
6H), 1.24−0.99 (m, 46H), 0.87−0.71 (m, 14H), 0.67−0.51 (m, 6H);
13
C NMR (125 MHz, CDCl3) δ: 179.8, 176.8, 170.8, 170.3, 151.7,
150.6, 144.2, 142.6, 140.8, 138.2, 134.0, 133.7, 131.7, 131.1, 130.1,
127.1, 126.9, 125.2, 122.9, 122.7, 119.5, 113.7, 110.8, 103.9, 88.6, 87.5,
58.9, 55.3, 50.7, 40.7, 40.4, 32.0, 31.9, 30.1, 29.8, 29.74, 29.70, 29.6,
29.42, 29.39, 29.35, 29.3, 29.2, 27.1, 24.3, 23.8, 22.7, 22.69, 14.2;
HRMS (ESI) m/z: [M + H]+ calcd for C72H99N2O4: 1055.7605; found:
1055.7596.
(E)-2-((E)-(7-Carboxy-1,1,3-trimethyl-1,3-dihydro-2H-benzo[e]-
indol-2-ylidene)methyl)-4-((3-decyl-1-hexyl-3,9,9-trioctyl-3,9-
dihydroindeno[1,2-f ]indol-1-ium-2-yl)methylene)-3-oxocyclobut-
1-en-1-olate (XSQ4). Started with 6b (0.18 g, 0.22 mmol) and 12
(0.156 g, 0.43 mmol). Yield: 0.100 g, 54%. 1H NMR (500 MHz,
CDCl3) δ: 8.77 (s, 1H), 8.35−8.15 (m, 2H), 8.01 (d, J = 6.1 Hz, 1H),
7.75 (d, J = 7.4 Hz, 1H), 7.60 (s, 1H), 7.40−7.29 (m, 4H), 6.96 (s, 1H),
6.24 (s, 1H), 6.07 (s, 1H), 4.17 (s, 2H), 3.66 (s, 3H), 3.16 (s, 2H), 2.14
(s, 6H), 2.10−2.01 (m, 4H), 2.01−1.94 (m, 2H), 1.92−1.85 (m, 2H),
1.49−1.43 (m, 2H), 1.36−1.27 (m, 4H), 1.23−1.18 (m, 6H), 1.16−
1.05 (m, 37H), 0.88 (t, J = 7.0 Hz, 3H), 0.85−0.75 (m, 15H), 0.72−
0.48 (m, 8H); 13C NMR (125 MHz, CDCl3) δ: 179.1, 175.4, 170.56,
170.13, 170.0, 151.5, 150.6, 144.0, 142.6, 140.8, 139.0, 139.0, 138.2,
135.4, 133.9, 131.6, 131.1, 130.1, 127.1, 126.9, 125.5, 123.5, 122.8,
122.6, 119.5, 114.2, 113.7, 110.7, 104.4, 88.5, 87.3, 58.9, 55.2, 50.6,
40.7, 32.0, 31.96, 31.9, 31.8, 30.1, 29.7, 29.6, 29.5, 29.4, 29.3, 29.2, 27.7,
27.2, 24.3, 23.9, 22.7, 22.7, 22.4, 14.2, 14.1; HRMS (ESI) m/z: [M +
H]+ calcd for C77H109N2O4: 1125.8387; found: 1125.8378.
■
ASSOCIATED CONTENT
*
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acsami.8b09866.
J−V curve, IPCE trace, Nyquist plots, photovoltaic
parameters, and EIS data of XSQ1−4-based dye cells,
dye desorption curves, materials and methods, synthetic
procedure, 1H and 13C NMR spectra (PDF)
■
AUTHOR INFORMATION
Corresponding Author
*E-mail: j.nithyanandhan@ncl.res.in.
DOI: 10.1021/acsami.8b09866
ACS Appl. Mater. Interfaces 2018, 10, 26335−26347
ACS Applied Materials & Interfaces
ORCID
Rajesh Bisht: 0000-0003-0150-9696
Jayaraj Nithyanandhan: 0000-0002-3429-4989
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
Funding from NWP0054 (CSIR-TAPSUN) and SERB-EMR/
2016/007114, India, is sincerely acknowledged. R.B. and V.S.
thank CSIR, New Delhi, India, and N.K. thanks UGC, New
Delhi, India, for research fellowships. J.N. thanks Dr.
Kothandam Krishnamoorthy, PSE Division, CSIR-NCL, Pune,
for his help with device fabrication.
■
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26347 DOI: 10.1021/acsami.8b09866

ACS Appl. Mater. Interfaces 2018, 10, 26335−26347