Sterically demanded unsymmetrical zinc phthalocyanines for dye-sensitized solar cells

Article abstract of DOI:10.1016/j.dyepig.2013.04.007

Three new sterically demanding unsymmetrical zinc phthalocyanines have been designed and synthesized as sensitizers for dye-sensitized solar cells. All three unsymmetrical phthalocyanines have been completely characterized by elemental analyses, mass spec

Full text of DOI:10.1016/j.dyepig.2013.04.007

Accepted Manuscript
Sterically demanded unsymmetrical zinc phthalocyanines for dye-sensitized solar
cells
L. Giribabu, V.K. Singh, Tejaswi Jella, Y. Soujanya, Anna Amat, Filippo De Angelis,
Aswani Yella, Peng Gao, Mohammad Khaja Nazeeruddin
PII:
S0143-7208(13)00134-4
10.1016/j.dyepig.2013.04.007
DYPI 3906
DOI:
Reference:
To appear in: Dyes and Pigments
Received Date: 12 December 2012
Revised Date: 1 April 2013
Accepted Date: 5 April 2013
Please cite this article as: Giribabu L, Singh VK, Jella T, Soujanya Y, Amat A, De Angelis F, Yella A,
Gao P, Nazeeruddin MK, Sterically demanded unsymmetrical zinc phthalocyanines for dye-sensitized
solar cells, Dyes and Pigments (2013), doi: 10.1016/j.dyepig.2013.04.007.
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ACCEPTED MANUSCRIPT
Sterically Demanded Unsymmetrical Zinc Phthalocyanines for Dye-
Sensitized Solar Cells
L. Giribabu, V.K. Singh, T. Jella, Y. Soujanya, Anna Amat, Filippo De Angelis, Aswani
Yella, Peng Gao, Mohammad Khaja Nazeeruddin
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
N
N
N
O
O
O
O
N
N
N
N
N
NZn
N
N
N
N
N
Zn
N
N
N
N
Zn
N
N
O
N
O
N
N
N
COOH
O
O
O
O
COOH
COOH
O
O
O
HOOC
COOH
O
O
O
O
O
DMPCH-1
DMPCH-2
DMPCH-3
Three new sterically demanded unsymmetrical zinc phthalocyanines have been designed,
synthesized and characterized for dye-sensitized solar cell applications.

ACCEPTED MANUSCRIPT
Sterically demanded unsymmetrical zinc phthalocyanines for dye-
sensitized solar cells
a*
a
a
b
c,d
c
L. Giribabu, V.K. Singh, Tejaswi Jella, Y. Soujanya, Anna Amat, Filippo De Angelis,
e
e
e
Aswani Yella, Peng Gao, Mohammad Khaja Nazeeruddin
a
Inorganic & Physical Chemistry Division, CSIR-Indian Institute of Chemical Technology,
Hyderabad-500607, India. Tel.: +91-40-27191724; fax: +91-40-27160921; e-mail:
giribabu@iict.res.in
b
Molecular Modelling Group, CSIR-Indian Institute of Chemical Technology, Hyderabad-
5
00067, Indi
c
Computational Laboratory for Hybrid/Organic Photovoltaics (CLHYO), Istituto CNR di
Scienze Tecnologie Molecolari, Via Elce di Sotto 8, I-06123, Perugia, Italy
d
Dipartimento di Chimica, Università di Perugia, Via elce di Sotto 8, 06213 Perugia, Italy
e
Laboratory for Photonics and Interfaces, Institute of Chemical Sciences and Engineering,
School of basic Sciences, Swiss Federal Institute of Technology, CH - 1015 Lausanne,
Switzerland.
ABSTRACT
Three new sterically demanding unsymmetrical zinc phthalocyanines have been designed and
synthesized as sensitizers for dye-sensitized solar cells. All three unsymmetrical
phthalocyanines have been completely characterized by elemental analyses, mass
1
spectrometry, FT-IR, H NMR, UV-Visible, and fluorescence (steady-state and life-time)
spectroscopies as well as electrochemical methods. Photophysical properties (absorption,
emission and redox properties) indicate that the LUMO of unsymmetrical phthalocyanines
2
lies above the TiO conduction band and HOMO is below the redox electrolyte. The
experimental results are supported by DFT/TD-DFT studies. Electrochemical and in-situ
spectroelectrochemical studies suggest that the redox reactions belong to the macrocyclic
ring-based electron transfer processes. All three unsymmetrical phthalocyanines were tested
-
-
3
in DSSC using I /I redox electrolyte system.
Keywords: Dye-Sensitized solar cells, Phthalocyanine, Unsymmetry, Absorption,
Spectroelectrochemistry, Redox Electrolyte.
1

ACCEPTED MANUSCRIPT
1
. Introduction
The world is rapidly approaching a precarious environmental state owing to the extensive use
of fossil fuels, which may be depleted in the near future. In this regard, solar energy is
expected to play a key role in sustainable development [1]. Among the various photovoltaic
technologies, dye-sensitized solar cells, (DSSC) have emerged alongside conventional p-n
junction solar cells [2-4]. In a typical DSSC, upon photo excitation, the dye injects an
electron into the conduction band of a nanocrystalline film of a wide-band-gap oxide
semiconductor, such as titanium dioxide (TiO
ground state by electron donation from a redox couple. Energy conversion efficiencies up to
1.4% have been achieved using Ru(II) polypyridyl complexes as molecular sensitizers [5-6].
2
), and is subsequently regenerated back to the
1
However, Ru(II) polypyridyl complexes are expensive to the rarity of the metal in the earth’s
crust and also they lack strong absorption in the red or near-infrared region (NIR), where the
solar flux of photons is still significant, thus limiting the realization of high efficient devices.
For this reason, dyes with large π-conjugated systems such as porphyrins and
phthalocyanines are receiving considerable attention for sensitization of nanocrystalline TiO
2
in view of their efficient electron transfer process [7-9]. Recently, Grätzel, Diau, and Yeh et
al. have reported a DSSC with an incorporated porphyrin dye having a cell performance that
achieves with an efficiency of 12.3% [10].
Phthalocyanine (Pc) derivatives are also suitable DSSC sensitizers because of their
intense and tunable absorption in the red to NIR, transparency over a large portion of the
visible spectrum, and extraordinary thermal as well as photochemical stability [11-12].
However, the efficiencies of DSSC employing phthalocyanines as sensitizers have not been
impressive. This is mainly due to the fact that the phthalocyanine molecule has strong
2
tendency to aggregate on the TiO surface and also a lack of directionality of the electron
transfer in the excited state. Nazeeruddin and co-workers reported an unsymmetrical
amphiphilic zinc phthalocyanine (PCH001, see Figure 1) having three bulky tert-butyl
groups, which minimizes the aggregation and two carboxylic acids in its molecular structure
showing an overall conversion efficiency of up to 3.05% [13-14]. Moreover, Mori et al.
recently confirmed that the presence of bulky substituents at peripheral positions of
phthalocyanine macrocyle, completely suppress aggregation and, therefore achieved high
energy conversion efficiency of 4.6% [15]. The carboxyl-functionalized zinc phthalocyanine
substituted at the periphery with six 2,6-diphenylphenoxy groups achieved up to a 4.6 %
2

ACCEPTED MANUSCRIPT
conversion efficiency. Recently, Torres and co-workers have extended this concept and
introduced more rigid π-conjugated bridges (either C=C or C≡C bond) between the anchoring
carboxyl groups and the phthalocyanine macrocycle with an overall conversion of up to
6
.13% [16].
In this manuscript, as part of our efforts to investigate further improvement of
efficiency of DSSC devices based on phthalocyanine sensitizers, we report the synthesis and
photovoltaic characterizations of a series of sterically demanded phthalocyanines (DMPCH-
1
, DMPCH-2 and DMPCH-3) shown in Figure 1. DMPCH-1&2 differ in having number of
anchoring groups and DMPCH-3 possesses a different donor moiety. All the sensitizers have
1
been completely characterized by elemental analyses, Mass, H NMR, UV-Vis and emission
spectroscopies (both steady-state and time-resolved), as well as cyclic voltammetry including
spectroelectrochemistry. The studied phthalocyanines have also been investigated
computationally by means of DFT and TDDFT theories. The introduction of 3,4-dimethoxy
phenyl and 2,6-dimethoxy phenyl at the six peripheral positions of the benzene rings of
phthalocyanine DMPCH-1&2 and DMPCH-3, respectively, is supposed to cause steric
crowding and hence reduce the aggregation, which will afford high power conversion. The
-
-
structures of three unsymmetrical phthalocyanines are shown in Figure 1. We have used I /I3
based redox electrolyte for the fabrication of devices.
2
. Experimental
4
,5-dichlorophthalnitrile, 3,4-dimethoxyphenyl boronic acid, 2,6-dimethoxy phenol, 1,8-
, K PO , and Zn(OAc) are procured from Aldrich
diazabicyclo[5.4.0]undec-7-ene, Pd(PPh
3
)
4
3
4
2
and were used as such. The solvents 1,4-dioxane, THF, 1-pentanol, and DMF were obtained
from BDH (India) and were purified prior to use [17]. Analytical grade ethanol was also
obtained from BDH and was used as such. Column chromatography was performed on
Aceme silica gel (60-120).
2
3
.1. Synthesis
,4-dimethoxy phenyl boronic acid (1), 3,4-dicyanobenzoic acid (3) and triester phthalonitrile
were synthesized as per the literature methods [18,19].
3

ACCEPTED MANUSCRIPT
2
.1.1. 4,5-Bis(3,4-dimethoxyphenyl) phthalonitrile (2):
Anhydrous 1,4-dioxane (20 mL) was taken in a 100 mL round bottom flask. To this charged
with 4,5-dichlorophthalonitrile (0.32 g, 1.62 mmol), 3,4-dimethoxyphenyl boronic acid (1.0
3 3 4
g, 5.5 mmol), P(o-Tolyl) (0.1 g, 0.323 mmol), K PO (2.05 g, 9.70 mmol) and then flushed
3 4
with nitrogen for 15 minutes before the addition of Pd(PPh ) (0.04 g, 0.032 mmol). The
0
reaction mixture was stirred at 90 C for 6 h under nitrogen atmosphere. After cooling to
room temperature, the reaction mixture was washed twice with water. The combined organic
layers were washed once with water, subsequently dried over anhydrous sodium sulphate,
filtered and concentrated by rotary evaporator. The resultant solid material was subjected to
silica gel column chromatography and eluted with hexane-ethyl acetate to obtain the desired
product as yellow powder in 67% yield (0.44 g). FT-IR (KBr) υmax 2928, 2223 (CN), 1254,
-
1 1
1
2
024 cm . H NMR (300 MHz, CDCl
3
): δ (ppm) 7.76 (s, 2H), 6.62-6.78 (m, 4H), 6.47 (s,
+
H), 3.82 (s, 6H), 3.56 (s, 6H); EI-MS (m/z): C24
H
20
N
2
O
4
[400.14]: M 400. Elemental
20 2 4
analysis of Anal. Calcd. For C24H N O % (400.14): C, 71.99; H, 5.03; N, 7.00. Found: C,
7
1.95; H, 5.03; N, 6.95.
2
.1.2. DMPCH-1:
Anhydrous 1-pentanol (5 mL) was taken in 25 mL RB flask. To this was added 2 (1.0 g, 2.5
mmol), 3 (0.15 g, 0.84 mmol) and Zn(OAc) (0.24 g, 1.092 mmol) was under nitrogen
2
atmosphere. 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) (0.1 mL, 0.66 mmol) was added at
0
0
1
00 C and the resultant solution was heated to 140 C for 20 h and then cooled to room
temperature. Pentanol was removed under high vacuum and the solid green material was
precipitated from methanol which was then subjected to silica gel column chromatography
and eluted with methanol-chloroform. The green phthalocyanine compound (second fraction)
obtained was reprecipitated from methanol to afford the pure compound in 8% yield (0.097
-1
g) for this isomer. FT-IR (KBr) υmax 3413, 2928, 2840, 1713, 1254, 1024 cm . UV-Vis: (in
-1
-1
THF, λmax, ε M cm ): 691(91,100), 623(18,200), 354(34,800). ESI-MS (m/z):
+
C
C
81
81
H
H
64
64
N
8
8
O
14Zn [1436.38]: [M-H] 1435. Elemental analysis of Anal. Calcd. For
14Zn % (1436.38): C, 67.62; H, 4.48; N, 7.79. Found: C, 67.71; H, 4.52; N, 7.94.
N
O
2
.1.3. DMPCH-2:
4

ACCEPTED MANUSCRIPT
Anhydrous 1-pentanol (5 mL) was taken in 25 mL RB flask. To this was added 2 (1.0 g, 2.5
mmol), 4 (0.310 g, 0.84 mmol) and Zn(OAc) (0.240 g, 1.092 mmol) under nitrogen
2
0
atmosphere. To this catalytic amount of DBU (0.1 mL, 0.66 mmol) was added at 100 C and
0
the resultant solution was heated to 140 C for 20 h and cooled to room temperature. Pentanol
was removed under high vacuum. Solid material obtained was subjected to silica gel column
chromatography and eluted with hexane-chloroform. The second fraction was collected and
reprecipitated from methanol to get 5 in 9% yields (0.12 g) for this particular isomer. FT-IR
-1
(
KBr) υmax 2930, 2839, 1728 (CO stretching), 1249, 1026 cm . ESI-MS (m/z):
+
C
91
H
80
N
8
O
18Zn [1639]: (M ) 1640. Elemental analysis of Anal. Calcd. For C91
H
80
N
8
O18Zn %
(1639.05): C, 66.68; H, 4.92; N, 6.84. Found: C, 66.65; H, 4.95; N, 6.85.
The desired compound was obtained by the hydrolysis of 5 using Na/Ethanol. 100 mg
of compound 5 was dissolved in 30 mL of ethanol. To this 1 g (43.3 mmol) of sodium was
added. The resulting reaction mixture was stirred at room temperature for 7 days under
nitrogen atmosphere. The solvent was removed under reduced pressure. The obtained solid
material was dissolved in water and the pH was adjusted to 2-3 by adding dil. HCl. The
precipitate was filtered and dried under vacuum to get the desired product in 92% yield (0.85
-1
-1
-1
g). FT-IR (KBr) υmax 1719 (CO stretching) cm . UV-Vis: (in THF, λmax, ε M cm ):
+
6
1
4
91(1,35,100), 623 (24,500), 355 (47,600). ESI-MS (m/z): C H N O Zn [1510]: (M )
8
4
68
8
16
511.5, Elemental analysis of Anal. Calcd. For C84
.54; N, 7.42. Found: C, 66.75; H, 4.50; N, 7.45.
68 8
H N O16Zn % (1510.87): C, 66.78; H,
2
.1.4. 4,5-Bis(2,6-dimethoxyphenoxy) phthalonitrile (6):
Dry DMF (15 mL) was taken in 50 mL RB flask. To this was added 2,6-dimethoxyphenol
2 3
(3.126 g, 20.30 mmol), 4,5-dichlorophthalonitrile (1.0 g, 5.076 mmol), K CO (7.015 g,
o
5
0.76 mmol) and the resultant reaction mixture was heated at 100 C under nitrogen
atmosphere for 48 h. The reaction mixture was poured into water and the aqueous layer was
extracted three times with dichloromethane and dried over anhydrous Na SO . The organic
2
4
layer was evaporated and the residue was purified by silica gel column chromatography by
eluting with Hexane-Ethyl acetate to get the pure compound as white solid in 85% yield (1.85
-1 1
g). FT-IR (KBr) υmax 2229 (CN) cm . H NMR (CDCl
3
, 300MHz): δ (ppm) 7.9 (s, 2H), 6.9
(
s, 2H), 6.82(d, J= 8.30 Hz, 4H), 3.78 (s, 12H). ESI-MS (m/z): C H N O [432.13]: (M+1)
2
4
20
2
6
4
33.
5

ACCEPTED MANUSCRIPT
2
.1.5. DMPCH-3:
Anhydrous 1-pentanol (10 mL) was taken in 25 mL RB flask. To this was added 4,5-bis(2,6-
dimethoxyphenoxy)phthalonitrile (0.900 g, 2.08 mmol), 4-(1,1,2-tricarbethoxyethyl)
2
phthalonitrile (0.260 g ,0.695 mmol), Zn(OAc) (0.240 mg ,0.9 mmol) and catalytic amount
of DBU and the reaction mixture was heated under reflux for 20 h under nitrogen
atmosphere. The solvent was then removed under reduced pressure and the green solid
material obtained was subjected to column chromatography using silica gel (100-200 mesh)
by eluting with CHCl
3
-Hexane. The second green band was collected as the desired product
(7) and recrystallized from methanol to obtain the pure compound in 8% yield (0.10 g) for
-1
83 8
this particular isomer. FT-IR (KBr) υmax 1727 (-COOEt) cm . ESI-MS (m/z): C92H N O24Zn
+
[
1748.48]: M 1748.
The desired unsymmetrical phthalocyanine was obtained by hydrolysis of 7 using
Na/Ethanol. Ethanol (20 mL) was taken in a dry two neck RB flask and to this 1 gm (43.4
mmol) of sodium was added and allowed to dissolve. Then 100 mg of 7 was dissolved in
THF-Ethanol solvent mixture. The resulting reaction mixture was stirred at room temperature
for 7 days. The solvent was evaporated under reduced pressure. The obtained solid material
was dissolved in water and pH was adjusted to 2-3 by using dil.HCl. The precipitate was
filtered and dried under reduced pressure to get the desired product in 80% yield (0.086 g).
-
1
+
FT-IR (KBr) υmax 1713 (-COOH) cm . ESI-MS (m/z): C84
H
68
N
8
O
22Zn [1606.87]: [M-2H]
604, UV-Vis: (in DCM, λmax, ε M cm ): 686 (1,50,000), 649 sh (31,000), 614 (36,000),
60 (85,000). For C84 22Zn % (1606.87): C, 62.79; H, 4.27; N, 6.97. Found: C, 62.84;
-
1
-1
1
3
68 8
H N O
H, 4.22; N, 6.99.
.2. Methods
The UV-Visible spectra were recorded with Ocean Optics spectrophotometer using for 1 x
2
-6
1
0 M solutions in THF solvent. Steady state fluorescence spectra were recorded using a
Spex model Fluorlog-3 spectrofluorometer for solutions having optical density at the
wavelength of excitation (λex) ≈ 0.11. Time-resolved fluorescence measurements have been
carried out using HORIBA Jobin Yvon spectrofluorometer. Briefly, the samples were
excited at 370 nm and the emission was monitored at 700 nm, in all unsymmetrical
3
4 -1
phthalocyanines. The count rates employed were typically 10 – 10 s . Deconvolution of the
data was carried out by the method of iterative reconvolution of the instrument response
6

ACCEPTED MANUSCRIPT
function and the assumed decay function using DAS-6 software. The goodness of the fit of
the experimental data to the assumed decay function was judged by the standard statistical
tests (i.e., random distribution of weighted residuals, the autocorrelation function and the
2
1
values of reduced χ ). H NMR spectra were obtained at 300 MHz using a Brucker 300
Avance NMR spectrometer running X-WIN NMR software. The elemental analyses were
done on an Elementar, Vario MICRO CUBE analyzer.
Differential pulse and cyclic voltammetric measurements were performed on a PC-
controlled CH instruments model CHI 620C electrochemical analyzer. Cyclic voltammetric
experiments were performed on 1 mM unsymmetrical phthalocyanine solution in THF
solvent at scan rate of 100 mV/s using 0.1 M tetrabutyl ammonium perchlorate (TBAP) as
supporting electrolyte. The working electrode is glassy carbon, standard calomel electrode
(SCE) is reference electrode and platinum wire is an auxiliary electrode. After a cyclic
voltammogram (CV) had been recorded, ferrocene was added, and a second voltammogram
was measured. Spectroelectrochemical experiments were performed using a CH instruments
model CHI 620C electrochemical analyzer utilizing a three-electrode configuration of thin
layer quartz spectroelectrochemical cell at 25 °C. The working electrode was transparent Pt
gauze. Pt wire counter electrode and SCE reference electrode separated from the bulk of the
solution by a double bridge were used. The TG curves of the samples were performed on a
c
thermogravimetric analyzer Mettler Tolledo TGA/SDTA 851 under nitrogen atmosphere
o
o
(
99.999%) from 25 to 600 C, in Al O crucibles. The heating rates were 10 C/min and the
2 3
flow rate of nitrogen was 80 mL/min.
2
.2.1. Dye cell preparation
2
The detailed TiO
2
photoelectrode (area: ca. 0.740 cm ) preparation was described in our
earlier studies [20,21]. Briefly, nanocrystalline TiO
2
films of 8 – 10 µm thickness with
porosity of 68% were deposited onto transparent conducting glass (Nippon Sheet Glass,
which has been coated with a fluorine-doped stannic oxide layer, sheet resistance of 8-10
2
Ω/cm ) over which ~4.5 µm thickness of 400 nm anatase TiO
2
particles (CCIC, HPW-400) as
o
scattering layer by screen-printing. These films were gradually sintered at 500 C for 30 min.
The heated electrodes were impregnated with a 0.04 M titanium tetrachloride solution in
o
water saturated desiccator for 30 min at 70 C and then washed with distilled water and rinsed
o
with ethanol. The electrodes were heated again at 500 C for 30 min and then allowed to cool
7

ACCEPTED MANUSCRIPT
o
-6
to 50 C before dipping them into the dye solution (3 x 10 M in THF). The electrodes were
o
dipped into the dye solution for >18 h at 25 C. The dye sensitized TiO electrodes were
2
assembled with Pt counter electrodes by heating with a hot-melt surlyn film (Surlyn 1702, 25
µm thickness, Du-Pont) as a spacer in-between the electrodes. A liquid electrolyte, consisted
of 0.6 M 1,3-dimethylimidazolium iodide, 0.03 M iodine, 0.05 M LiI, 0.05 M guanidinium
thiocyanate, and 0.25 M 4-tert-butylpyridine in 15/85 (v/v) mixture of valeronitrile and
acetonitrile was filled through the predrilled hole present on the counter electrode and then
the hole was sealed with a Surlyn disk and a thin glass to avoid leakage of the electrolyte.
The photovoltaic performance of these devices were characterized under irradiation
source of 450 W xenon light source (Osram XBO 450, U.S.A.), which is equivalent to an AM
1
.5 solar simulator and was calibrated by using a Tempax 113 solar filter (Schott). In order to
reduce scattered light from the edge of the glass electrodes of the dyed TiO layer, a light
2
shading black mask was used onto the DSSCs. For photovoltaic measurements of the DSSCs,
the irradiation source was a 450 W xenon light source (Osram XBO 450, Germany) with a
filter (Schott 113), whose power was regulated to the AM 1.5G solar standard by using a
reference Si photodiode equipped with a color matched filter (KG-3, Schott) in order to
reduce the mismatch in the region of 350-750 nm between the simulated light and AM 1.5G
to less than 4%. The measurement of incident photon-to-current conversion efficiency (IPCE)
was plotted as a function of excitation wavelength by using the incident light from a 300 W
xenon lamp (ILC Technology, USA), which was focused through a Gemini-180 double
monochromator (Jobin Yvon Ltd.). The measurement settling time between applying a
voltage and measuring a current for the I-V characterization of DSSCs was fixed to 40 ms.
2
.3. Computational methodology
DFT and TD-DFT calculations have been carried in solution (THF) using the Gaussian09
code [22]. The Becke’s hybrid exchange functional B3 [23] with the Lee–Yang–Parr
correlation functional LYP [24,25] (B3LYP) have been used in our calculations together with
the 6-31G** basis set. [26] The solvation effects have been included by means of the
conductor-like polarizable continuum model CPCM [27-29]. The lowest 100 singlet-singlet
excitations have been computed on the fully optimized geometries and transition energies and
oscillator strengths convoluted with a Gaussian function of sigma=0.20.
3
. Results and Discussions
8

ACCEPTED MANUSCRIPT
The syntheses of the new sterically demanded unsymmetrical phthalocyanines are
shown in schemes 1 & 2. The phthalonitrile, 4,5-bis(3,4-dimethoxy) phthalonitrile (2) was
synthesized by using a Suzuki coupling reaction [30]. In contrast, the phthalonitrile, 4,5-
bis(2,6-dimethoxyphenoxy) phthalonitrile (6) was synthesized by an aromatic nucleophilic
substitution reaction between 2,6-dimethoxy phenol and 4,5-dichlorophthalonitrile. All three
sterically demanded unsymmetrical phthalocyanines were synthesized by cross-condensation
of two different phthalonitriles. For example, DMPCH-1 was synthesized by cross-
2
condensation of 2 and 3 using Zn(OAc) as metal template. On the other hand DMPCH-2 &
3
was obtained by cross-condensation of 4 with either 2 or 6 phthalonitriles, respectively. In
all three unsymmetrical phthalocyanines, six different isomers were formed but, we have
isolated only the required isomer (i.e., A3B) and remaining isomers were discarded [31]. The
1
new unsymmetrical phthalocyanines were characterized by elemental analysis, Mass, IR, H
NMR, and fluorescence spectroscopies (both steady-state and time-resolved) as well as cyclic
voltammetry (including spectroelectrochemistry).
The mass spectrum of each of unsymmetrical phthalocyanine shows the molecular
ion peak, which correspond to the presence of respective unsymmetrical phthalocyanine.
Figure 2 shows the absorption spectra of all three unsymmetrical phthalocyanines using THF
solvent and the corresponding data are presented in Table 1. The UV-Visible absorption
spectroscopy is a very valuable technique which can be used to study the aggregation
phenomena of phthalocyanines in both solution and solid state. As frequently encountered in
most phthalocyanines, the shoulder on the high energy side of the Q-band indicates the
presence of aggregated species [32,33]. As shown in Figure 2, all three unsymmetrical
phthalocyanines have shown a very intense Q-band whereas the band at higher energy side of
the Q-band is very low intensity. This clearly indicates that the aggregation of these
unsymmetrical phthalcoyanines in THF solution is low. Moreover, the theoretical absorption
spectra computed on the monomers are in very good agreement with the experimental ones
further confirming the low presence of aggregates in THF solution. Absorption spectra of
DMPCH-3 shows split in the Q-band region. This is probably due to the presence of more
bulky groups in DMPCH-3 than other unsymmetrical phthalocyanines. A similar split in Q-
bands was also observed in other sterically hindered unsymmetrical phthalocyanines [16].
Figure 3 represents the emission spectra of all three unsymmetrical phthalocyanines obtained
at room temperature in THF solvent. The emission maxima were presented in Table 1. The
9

ACCEPTED MANUSCRIPT
excitation spectrum obtained by exciting emission maximum at 765 nm shows a maximum at
6
97 nm and E0-0 energy of these unsymmetrical phthalocyanines estimated from excitation
and emission spectra are 1.78, 1.79 & 1.80 eV for DMPCH-1, DMPCH-2 & DMPCH-3,
respectively. Quenched emission spectra were observed in all three unsymmetrical
phthalocyanines when adsorbed onto 2 µm thick TiO
2
layer as a consequence of electron
. The singlet
injection from the excited state of phthalocyanine into conduction band of TiO
2
excited life-time of all three unsymmetrical phthalocyanines were measured in THF solvent
and were found to be 2.70, 3.11 & 2.86 ns for DMPCH-1, DMPCH-2 & DMPCH-3,
respectively. In all three cases the excited state life-time quenched when adsorbed onto 2 µm
2
thick TiO layer.
With a view to evaluate the HOMO-LUMO levels of unsymmetrical
phthalocyanines, we performed the electrochemistry by using cyclic and differential pulse
voltammetric techniques in THF solvent. Each of unsymmetrical phthalocyanine undergoes
either reversible or quasireversible oxidation at 0.60, 0.65 and 0.80 Vs. SCE generating π-
cation radical for DMPCH-1, DMPCH-2 & DMPCH-3, respectively. The cyclic
voltammogram (CV, solid line) and differential pulse voltammogram (DPV, dotted line) of
DMPCH-1 are shown in Figure 4. In a similar manner each unsymmetrical phthalocyanine
undergoes either two or three reversible or quasireversible reductions (complete data in Table
1
). With respect to dye-sensitization of wide-band-gap semiconductors, e.g. TiO , the
2
oxidation potentials of unsymmetrical phthalocyanines and the E0-0 transition energy, the
energy levels of the singlet excited states (excited state oxidation potential) of DMPCH-1,
DMPCH-2 & DMPCH-3 were determined to be -1.18, -1.14 & -1.00 V vs. SCE,
respectively [34]. Whereas the energy level of the conduction band edge of TiO
V vs. SCE [35]. This makes electron injection from the excited state of unsymmetrical
phthalocyanines into the conduction band of TiO thermodynamically feasible. Furthermore,
the HOMO level of the unsymmetrical phthalocyanines is lower than the energy level of the
2
is ca. –0.74
2
-
-
redox couple I /I
3
(0.2 V vs. SCE) in the electrolyte, enabling the dye regeneration by
electron transfer from iodide ions in the electrolyte.
3
.1. Spectroelectrochemical Studies
Spectroelectrochemical studies were employed to monitor changes during redox
reactions as well as assignments in the CVs of unsymmetrical phthalocyanines. This
1
0

ACCEPTED MANUSCRIPT
information is essential concerning the durability of the sensitizer. Figure 5 shows the
spectral changes of DMPCH-2 under applied potential. During the controlled potential
oxidation of DMPCH-2 at 0.90 V applied potential, the absorption of both Q-band and Soret
band decreases in intensity without shift, while new bands appeared at 510 and 744 nm with
increase in intensity. The band assigned to the aggregated species at 623 nm is also decreases
in intensity due to the shifting of the aggregation-disaggregation equilibrium under applied
potential. During this electrochemical oxidation, clear isosbestic points are observed at 343,
4
13, 612, 639 and 713 nm, which demonstrates that oxidation gives a single product. These
spectroscopic changes indicate presence of aggregation-disaggregation equilibrium and a
II
2
II
-
-
macrocycle ring oxidation process and the oxidation process assigned to [Zn Pc ]/[Zn Pc
1
+1
]
process [36-38]. The unsymmetrical phthalocyanine return to their original absorption
spectrum, when the applied potential is removed. During the reduction of DMPCH-2
applied potential at -1.2 V), the absorption of the both the Q-band and Soret band intensities
(
increases without shift. In contrast, the intensity of the peak at 623 nm decreases, which
indicates disaggregation of the phthalocyanine macrocycle. During this process clear
isosbestic points are observed at 348, 401, 616 and 707 nm, which clearly indicates that the
reduction gives a single product. These changes are typical of the ring-based reduction and
II
2
II
3 -1
-
-
assigned to [Zn Pc ]/[Zn Pc ] . Spectroscopic changes under controlled potential
II
3 -1
-
application at -1.80 V supported the further reduction of the monoanionic [Zn Pc ] species
II
4 -2
-
to [Zn Pc ] . Similar spectroscopic changes are observed in the case of DMPCH-1 also
during the controlled applied potential (see Supplementary data).
Figure 6 indicates in-situ spectral changes of DMPCH-3 in THF solvent during the
applied potential. When the applied potential is at 0.90 V, the Q-band at 683 nm decreases in
intensity with a blue-shift to 679 nm. On the other hand the Soret band at 363 nm increases
the intensity with a blue-shift to 353 nm and appearance of a new band at 466 nm. This
process gives clear isosbestic points at 399, 624, & 676 nm in the spectra, which indicates the
oxidation process give a single product. Figure 6b represents the spectral changes during the
reduction process of the phthalocyanine macrocycle. During -1.0 V potential application, the
intensity of both the Q-band and the Soret band decreases with the change in absorption
II
2
II
1 +1
-
-
maxima. The reduction process assigned to [Zn Pc ]/[Zn Pc ] with isosbestic points at
1
1

ACCEPTED MANUSCRIPT
II
3 -1
-
3
32, 419, 607 & 701 nm. Further reduction of [Zn Pc ] at -1.70 V indicates further
decreases in intensity of the Q-band, whereas the Soret band becomes a shoulder with the
appearance of new band at 550 nm. This process gives the isosbestic points at 303, 398, 607,
6
32 & 711 nm. Both first and second reduction belongs to the macrocycle reductions.
3
.2. Computational Studies
To gain insight into the electronic and optical properties of the investigated
compounds, we performed DFT/TDDFT calculations in THF on the optimized geometries.
The results are reported in terms of schematic energy diagram and isodensity plots of frontier
molecular orbitals in Figure 7 and 8. The computed TDDFT absorption spectra absorption in
THF are compared to the experimental ones in Figure 9 while a survey of the most relevant
excited states are compiled in Table 2, 3 and 4.
From Figure 7 we notice the trends of HOMO energies reproduce the decreased (i.e.
less positive) oxidation potential measured for DMPCH-3 compared to DMPCH-1 and
DMPCH-2 which have almost the same oxidation potential. Also in line with
electrochemical measurements a higher lying LUMO is calculated for DMPCH-3 compared
to DMPCH-1 and DMPCH-2, probably as a result of the increased donation to the
macrocyle. For all the investigated systems the HOMO (H) is delocalized on the π-electron
system of the phthalocyanine ring while the LUMO (L) is a π* orbitals delocalized on the
phthalocyanine center and on the carboxyl group, Figure 8.
This electronic structure picture results in a lowest transition, S (H→L), with a
1
directional charge flow from the dye core to the anchoring group that facilitates the electron
injection from the excited state of phthalocyanine macrocyle sensitizer to the conduction
band of TiO . These results are in good agreement other phthalocyanine sensitizers reported
2
in the literature [39]. For all the species the low energy has also a contribution from the
2
second transition S that has a H→L+1 character and similar oscillator strength than that of
S
1
. In this transition the arriving state L+1 that is also a π* orbital delocalized on the
phthalocyanine center but contrarily to the L case it has no contribution from the anchoring
group. On the other hand, for the DMPCH-3, possessing two different carboxylic groups, the
charge delocalization of the LUMO extends only to one of the two groups and this could lead
to a loss in the charge generation with respect to that of DMPCH-1 and DMPCH-2
1
2

ACCEPTED MANUSCRIPT
depending on which is the preferred anchoring site. On overall, the computed spectra are in
good agreement with the experimental band though blue-shifted with respect to the
experiment, especially for the DMPCH-3 species. Calculations on the isolated molecule
models do not show the presence of the shoulder at ca. 630 nm confirming its assignment to
the phthalocyanines aggregates, based on the spectroelectrochemistry measurements, see
above.
3
.3. Photoelectrochemical Studies
Due to the favorable photophysical properties, electrochemical properties and the energy
profile with respect to the conduction band edge of TiO and the redox system, which are
further supported by our TD-DFT studies, the photovoltaic performance of unsymmetrical
phthalocyanines were evaluated by constructing DSSC using nanocrystalline TiO films and
2
2
-
3-
I /I redox electrolyte system and the results are shown in Table 5. The overall conversion
efficiency (η) is calculated from the JSC, VOC, FF and intensity of incident light (Iph), using the
equation below.
−2
J [mAcm ] .V [V]Xff
SC
OC
η[%] =
x100
Iph
As tabulated in Table 5, the short-circuit current density (JSC), open-circuit voltage (VOC), and
fill factor (ff) of DMPCH-2 based DSSC under an irradiance of AM 1.5G are 3.26 mA/cm2,
0
.604 V and 0.67, respectively, yielding an overall conversion efficiency of 1.07%. Similarly,
we have observed an overall conversion efficiency of 0.89, & 0.74% using DMPCH-1, &
DMPCH-3 based sensitizers, respectively.
3
.4. Thermogravimetric studies
Finally, we have examined the thermal stability of the new unsymmetrical
phthalocyanines by using thermogravimetric analysis for outdoor applications. Figure 10
shows the thermal behavior of DMPCH-1. It is known from the literature that phthalocyanine
o
and its metallo derivatives are stable up to 400 C [40]. The thermograme indicates that the
o
DMPCH-1 sensitizer is stable up to 250 C. The initial weight loss (3.00 %) was observed in
o
1
50 - 300 C temperature and is attributed to the removal of moisture and after that weight
loss was due to the removal of the carboxyl group from the macrocycle. Similar
1
3

ACCEPTED MANUSCRIPT
thermogrames are obtained with DMPCH-2 & DMPCH-3 sensitizers (See supporting
information & Table 6).
4
. Conclusions
In conclusion, we have designed three sterically demanding unsymmetrical phthalocyanines
for dye-sensitized solar cells. The absorption maxima of these phthalocyanines are located at
6
90 nm in THF solvent and the emission maxima at around 700 nm with excited state life-
time of 2.70, 3.11 & 2.86 ns for DMPCH-1, DMPCH-2 & DMPCH-3, respectively. Both
emission intensity and excited state life-time was quenched when adsorbed onto TiO films, a
feature indicates that there is an efficient electron transfer from excited state of macrocycle to
TiO conduction band. Spectroelectrochemical studies indicate that the electron transfer
processes are ring-centered and not metal-centered processes. All three unsymmetrical
2
2
-
-
phthalocyanines were tested in DSSC using I /I redox couple and offered low overall
3
conversion efficiencies of ca. 1.1%.
Acknowledgements
The authors are thankful to the joint DST-EU project ‘ESCORT’ (FP7-ENERGY-2010,
contract no. 262910) for the financial support of this work. The author VKS thanks to CSIR
for senior research fellowship.
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(
1
8

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a
Table 1. UV-Visible, Emission and Electrochemical Data
b
c
d
Compound
Absorption
Emission
E0-0(eV)
Potential V vs. SCE
-
1
-1
λmax, nm (log ε M cm )
λmax, nm
Oxidation
0.60
Reduction
DMPCH-1 691(4.96), 623 (4.26), 354 701, 774
4.54).
1.78
1.79
1.80
-1.02, -1.60, -1.87
(
DMPCH-2 691(5.13), 623 (4.39), 355 699, 772
4.68).
0.65
-1.22, -1.67
(
e
e
DMPCH-3 686 (5.18), 649(sh) 614 688, 773
0.80
-0.96, -1.41
(4.56), 360 (4.93).
a
b
c
d
Solvent THF. Error limits: λmax, ± 1 nm, log ε, ± 10%. Error limits: ±0.05 eV. Error
limits, E1/2, ± 0.03 V, 0.1 M TBAP.
1
9

ACCEPTED MANUSCRIPT
Table 2. DMPCH-1 experimental and theoretical absorption maxima (nm/eV), computed
transitions (nm/eV), oscillator strengths and composition in terms of molecular orbitals.
Exp.
Calc.
Trans
F
MO
6
80/1.83
662/1.88
671/1.85 (S1)
0.6971
0.8291
93% H→ L
92% H→ L+1
6
2
54/1.90 (S )
6
3
20/2.00 (sh)
60/3.45
336/3.69
339/3.66 (S )
0.7472
0.5724
0.4065
57% H→ L+5
42
2
1% H-14→ L
32% H-14→ L
5% H→ L+5
69% H→ L+6
3
3
37/3.68 (S43
32/3.74 (S47
)
)
2
2
0

ACCEPTED MANUSCRIPT
Table 3. DMPCH-2 experimental and theoretical absorption maxima (nm/eV), computed
transitions (nm/eV), oscillator strengths and composition in terms of molecular orbitals.
Exp.
Calc.
Trans
F
MO
6
6
82/1.82 (S1)
56/1.89 (S2)
0.7442
0.8313
95% H→ L
93% H→ L+1
6
6
80/1.83
25/2.00 (sh)
668/1.86
4
1
7% H→ L+6
0% H-17→ L
3
3
41/3.64 (S45)
41/3.64 (S46)
0.2715
0.4370
2
2
1
1
4% H-17→ L+1
1% H-15→ L
0% H-18→ L
0% H→ L+5
3
60/3.45
336/3.69
2
8% H→ L+5
3
39/3.66 (S47)
0.2931
23% H-15→ L
2% H-16→ L
1
3
3
37/368 (S48)
34/3.72 (S50)
0.3080
0.5288
56% H-18→ L
60% H→ L+6
2
1

ACCEPTED MANUSCRIPT
Table 4. DMPCH-3 experimental and theoretical absorption maxima (nm/eV), computed
transitions (nm/eV), oscillator strengths and composition in terms of molecular orbitals.
Exp.
Calc.
Trans
F
MO
7
6
6
4
20/1.72
665/1.86
620/2.00
665/1.86
620/2.00
0.7171
0.5801
97% H→ L
94% H→ L+1
89/1.80
23/1.99 (sh)
00-500/3.10-2.48 456/2.72 (sh)
472/2.63
0.2709
52% H-3→ L
1
1
9% H-2→ L
7% H-1→ L
4
44/2.79
0.2490
90% H-3→ L+1
76% H-19→ L
56% H-19→ L+1
3
75/3.31
336/3.69
361/3.43 (S ) 0.2730
38
3
48/3.56 (S44) 0.2818
2
1% H-22→ L+1
3
39/3.65 (S48) 0.3371
45% H-21→ L
2
1
6% H-20→ L
2% H-3→ L+2
3
27/3.79 (S52) 0.5716
48% H-20→ L+1
1
1
1% H→ L+4
0% H→ L+5
2
2

ACCEPTED MANUSCRIPT
a
Table 5: Photovoltaic performance data.
Dye
Light
JSC
VOC
Fill factor
η
Intensity
-2
a
a
[
mA cm ]
0.17
[V]
(ff)
[%]
DMPCH-1
DMPCH-1
DMPCH-1
DMPCH-2
DMPCH-2
DMPCH-2
DMPCH-3
DMPCH-3
0.1
0.5
1
0.449
0.500
0.518
0.383
0.463
0.604
0.441
0.488
0.504
0.75
0.75
0.74
0.38
0.64
0.67
0.74
0.75
0.61
1.00
1.94
0.30
1.66
3.26
0.22
1.20
2.33
0.71
0.74
0.46
0.97
1.07
0.78
0.87
0.89
0.1
0.5
1
0.1
0.5
1
DMPCH-3
0.75
a
2
Photoelectrode: TiO
2
(8 + 4 µm and 0.158 cm ); Error limits: Short-circuit photocurrent
-2
density, JSC, ±0.1 mAcm , Open-circuit voltage, VOC, ±30 mV, Fill factor, ff ±0.03;
Electrolyte: 0.6 M 1,3-dimethylimidazolium iodide, 0.03 M iodine, 0.05 M LiI, 0.05 M
guanidinium thiocyanate, and 0.25 M 4-tert-butylpyridine in 15/85 (v/v) mixture of
valeronitrile and acetonitrile.
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3

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Table 6: Thermal decomposition data
Compound
Temperature
rang ( C)
Mass
calculated (%)
loss Mass
loss Tentative
assignment
o
found (%)
DMPCH-1
25-300
3
1.25
Removal moisture
3
00-600
25-220
20-600
25-220
20-600
23.33
3.45
4.39
Pc ring
DMPCH-2
DMPCH-3
1.19
Removal moisture
Pc ring
2
44.75
13.05
81.04
6.89
1.12
Pc ring
2
6.43
Pc ring
2
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Figure Captions:
Fig. 1: Molecular structures of unsymmetrical phthalocyanines.
_
____
…….
Fig. 2: UV-Visible spectra of (
) DMPCH-1, (------) DMPCH-2 & (
) DMPCH-3 in
THF solvent.
_
____
…….
Fig. 3: Emission spectra (
) DMPCH-1, (------) DMPCH-2 & (
) DMPCH-3 in THF
solvent excitation at 690 nm.
_
____
Fig. 4: Cyclic (
) and differential (------) pulse voltammograms of DMPCH-2.
Fig. 5: In-Situ UV-Vis spectral changes of DMPCH-2 a) Eapp = 0.9 V. b) initial part of the
spectral changes at Eapp = -1.0 V, c) final part of the spectral changes at Eapp = -1.70 V.
Fig. 6: In-Situ UV-Vis spectral changes of DMPCH-3 a) Eapp = 1.40 V. b) initial part of the
spectral changes at Eapp = -1.0 V, c) final part of the spectral changes at Eapp = -1.70 V.
Fig. 7: Schematic representation of the energy levels for DMPCH-1, DMPCH-2 and
DMPCH-3 in THF solution.
Fig. 8: Electronic distribution computed in THF for the first occupied/unoccupied molecular
orbitals of the studied species.
Fig. 9: Computed vs. experimental absorption spectra in THF for DMPCH-1 (top),
DMPCH-2 (center), DMPCH-3 (bottom).
o
Fig. 10: TG/DTG curves of DMPCH-1 with heating rate of 10 C min-1 under nitrogen.
Scheme 1: Synthetic schemes of DMPCH-1 & DMPCH-2.
Scheme 2: Synthetic scheme of DMPCH-3.
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O
O
O
O
O
O
O
O
O
O
O
O
O
O
N
N
Zn
N
O
O
N
N
N
N
N
N
N
N
N
Zn
N
N
N
N
COOH
O
O
COOH
COOH
O
O
O
O
O
O
DMPCH-1
DMPCH-2
O
O
O
O
O
O
N
O
O
O
O
N
N
N
O
O
Zn
N
N
N
N
N
N
N
N
N
Zn
N
N
O
N
O
O
O
O
COOH
COOH
COOH
COOH
O
DMPCH-3
PCH-001
Figure 1
2
6

ACCEPTED MANUSCRIPT
2.0
1.6
1.2
0.8
0.4
0.0
300
400
500
600
700
800
Wavelength (nm)
Figure 2
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7

ACCEPTED MANUSCRIPT
7
7
7
7
7
7
6x10
5x10
4x10
3x10
2x10
1x10
0
650
700
750
800
Wavelength (nm)
Figure 3
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8