Tetrahedron Letters 54 (2013) 3132–3136

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Tetrahedron Letters
journal homepage: www.elsevier.com/locate/tetlet

One-pot synthesis of metal free organic dyes containing different acceptor

moieties for fabrication of dye-sensitized solar cells
Manoharan Subbaiah a, Ramkumar Sekar a, Elumalai Palani b, Anandan Sambandam a,⇑
a
Nanomaterials and Solar Energy Conversion Laboratory, Department of Chemistry, National Institute of Technology, Trichy 620 015, India
b
Department of Chemistry, University of Delhi, Delhi 110 007, India

a r t i c l e i n f o a b s t r a c t

Article history: A series of metal-free organic dyes containing diphenylamine or diethylamine as a donor which is linked
Received 3 January 2013 to the acrylic acid or rhodanine-3-acetic acid as a acceptor and phenyl p-spacer were synthesized
Revised 1 April 2013 through one-pot Knoevenagel condensation reaction which are used as photosensitizers for the applica-
Accepted 3 April 2013
tion of dye-sensitized solar cell (DSSC). Photophysical, electrochemical and DSSC performances were
Available online 10 April 2013
studied for the synthesized dyes of which diphenylamine donor and acrylic acid acceptor based dye
(Ar-ma) show high electron life time and maximum power conversion efficiency under AM1.5 illumina-
Keywords:
tion (85 mW cm2). Electrochemical impedance spectroscopy results and its theoretical calculation are
DSSC
Diphenylamine
found to have good agreements with the DSSC output performance.
Acrylic acid Ó 2013 Elsevier Ltd. All rights reserved.
Electron life time

After the discovery of dye-sensitized solar cell (DSSC) by Gratzel
and co-workers in 1991,1 it is a most attractive and promising re-
search for many researchers to do photovoltaic conversion of solar
energy by modifying the components present in it. In particular,
the sensitizer plays a crucial role in DSSC for getting higher current
conversion efficiency and the well known sensitizer ‘ruthenium
dyes’ are very expensive and difficult to synthesize. Hence the metal
free organic dyes have more advantages such as high molar extinc-
tion coefficient, environmental friendliness, low cost and easy to
tune the photophysical and electrochemical behaviour of the dyes.
Recently, a number of metal-free organic dyes such as coumarin2,3
merocyanine,4 cyanine,5 indoline,6 hemicyanine,7,8 triphenyl-
amine,9,10 dialkylaniline,11 oligothiophene,12 phenothiazine13 and
carbazole14 based organic dyes as novel photosensitizers have been
developed and achieved the DSSC performance up to 5–9%. The
mentioned organic dyes possess a molecular structure of the elec-
tron-donating and electron-accepting groups bridged by the conju-
gated chain (D–p–A).15 While light shining on the D–p–A dye
molecules, intramolecular charge transfer takes place by flow of
electrons from the donor to acceptor through p-bridge and in addi-
tion, the acceptor carrying functional groups such as –COOH may
strongly bind to the TiO2 surface.16 For better electron injection,
the LUMO of the acceptor moiety should lie higher than the conduc-
tion band of the TiO2.17 For this purpose, the acceptor moiety of the
D–p–A molecules should be tuned to get better electron transfer
and as well as reach achievable efficiency. The most commonly used
⇑ Corresponding author. Tel.: +91 431 2503639; fax: +91 431 2500133.
E-mail addresses: sanand@nitt.edu, sanand99@yahoo.com (A. Sambandam).
acceptor is cyanoacrylic acid and however, the disadvantage is that
the presence of the nitrile group in the acceptor moiety increases
the acidity which in turn reduces the binding (anchoring) ability
on the semiconductor. Hence for a stronger binding on the TiO2,
an acceptor without nitrile functional group (less acidic) is a better
choice.18,19 Recently, Surya Prakash Singh et al.20 used acrylic acid as
an acceptor for DSSC, where they introduced acrylic acid group in
triphenylamine (TPA) moiety through a lengthy procedure. That
is, after formylation of TPA, three steps were followed ((1) Wittig
reaction. (2) Vilsmeier Haack formylation. (3) Oxidation). In order
to reduce such a lengthy synthetic pathway, here we followed a sim-
ple one-step Knoevenagel type condensation reaction2,21 by using
malonic acid as a starting compound to get the acceptor acrylic acid.
Likewise, four metal-free organic dyes containing diphenylamine
and diethylamine as donor which is linked to the acrylic acid and
rhodanine-3-acetic acid as acceptor through a phenyl p-spacer were
synthesized (see Scheme 1) and performed the structural character-
izations. Their photophysical properties, electrochemical properties
and theoretical (density functional theory; DFT) calculations were
deduced to support the fact that these molecules are capable of uti-
lizing as photosensitizers for DSSC’s applications. For acceptor com-
parison, rhodanine-3-acetic acid was chosen instead of acrylic acid.
The synthetic methods employed to obtain the desired organic
dyes (Al-ma, Al-rh, Ar-ma and Ar-rh) were shown in Scheme 1.
The aldehyde precursors (4-diethyl amino benzaldehyde and 4-
formyltriphenylamine) were successfully converted into the de-
sired dyes by one-pot Knoevenagel condensation reaction of active
methylene compounds (malonic acid and rhodanine-3-acetic
acid).22 In the 1H NMR spectra of Al-ma dye, the hydrogen presented

0040-4039/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.tetlet.2013.04.012
 M. Subbaiah et al. / Tetrahedron Letters 54 (2013) 3132–3136 3133

a
N

OH
Ar-ma
N O

b
N
O S
S O
N
OH
O Ar-rh
a
N O

O
Al-ma OH
N

S
S O
b N
N OH
O
Al-rh
Scheme 1. Synthetic pathway of the organic dyes. (a) Malonic acid, piperidine, CH3CN, reflux. (b) Rhodanine-3-acetic acid, NH4OAc, AcOH, reflux.

confirmed by 1H NMR spectra (because these protons also show

Figure 1. ORTEP representation of the title compound Al-ma with displacement
ellipsoids drawn at the 50% probability level for nonH atoms.
in the C2 and C3 carbon shows doublet peak in the region of 7.72 and
6.21 ppm with coupling constant of 15.5 Hz which implies the dou-
ble bond (C(2)@C(3)) exists in E-conformation with respect to phe-
nyl and carboxylic acid group. This was further supported by X-ray
crystallography study. Similarly, the double bond (C(2)@C(3)) pre-
sented in Ar-ma dye also exists in E-conformation which is also
doublet peaks with coupling constant of 15.5 Hz). All the spectral
data of Al-rh and Ar-rh dyes were matched with already published
data.23,24
In order to understand the structure, bonding and conformation
around the Al-ma dye, the single crystal X-ray structural analysis
was carried out at 293 K. The single crystals of Al-ma dye were grown
from ethanol. The crystal structure of Al-ma is depicted in Figure 1
and additional crystallographic data are given in the supporting
information. The crystal structure shows the dye molecule was
arranged almost in the same plan. This planarity provides excellent
p-conjugation which allows an electron flow from the donor to
the acceptor group. The molecule Al-ma crystallizes in the mono-
clinic crystal system in P21/c space group. The C(2)@C(3) double
bond exists in E-conformation with respect to phenyl and
carboxylic acid group (dihedral angle sC(aryl)–C@C–C(OCOH): 179.299°).
Further, interestingly the molecule exists as dimer through
intermolecular O–H  O hydrogen bond. The distance between the
two oxygens forming the hydrogen bond is 2.631 Å (bond angle is
172.93°). In addition, the molecule is stabilized by intermolecular
C–H  O hydrogen bond which grows in a ladder like structure as
illustrated in Figure S1 (supporting information).

Table 1
Optical, electrochemical data and HOMO, LUMO energy levels of synthesized dyes

Dye kabs/nm (e/M1 cm1)a kem (nm)a EHOMO (eV)b E0–0 (eV)c ELUMO (eV)d Eox/V (Vs.Fc)
Al-ma 364 (28,121) 450 4.91 2.95 1.96 0.71
Ar-ma 369 (35,294) 452 5.04 2.69 2.35 0.84
Al-rh 469 (45,201) 543 5.02 2.41 2.61 0.82
Ar-rh 458 (35,750) 557 5.09 2.28 2.81 0.89
a
Absorption and emission spectra were measured in ethanol.
b
The oxidation potential of the dyes was measured under the following conditions: GC working electrode, 0.1 M TBAP in DMF as an electrolyte, scan rate of 100 mV/s.
c
The E(0–0) are estimated from the intercept of the absorption and emission spectra.
d
The excited state oxidation potentials were derived from the equation: E(LUMO) = E(HOMO)  E(0–0).
3134 M. Subbaiah et al. / Tetrahedron Letters 54 (2013) 3132–3136
In order to determine the photophysical properties of the syn-
thesized dyes, the electronic absorption and fluorescence emission
spectral studies were performed in ethanol medium (5  105 M).
The optical parameters deduced from these spectral studies are
listed in Table 1 and their corresponding spectra are shown in Fig-
ure S2 (supporting information). Each of these compounds exhibits
two major absorption peaks in the spectra: one weak absorption
band in the ultraviolet region of 230–330 nm corresponding to
the p–p⁄ electronic transitions and the prominent red-shifted band
appearing in the visible range of 360–470 nm is assigned to an
intramolecular charge transfer (ICT) between the donor unit and
the acceptor end group.25 Among the synthesized dyes, the rhoda-
nine-3-acetic acid acceptor based dye shows high maximum
absorption wavelength (kmax) with highest molar extension coeffi-
cient (e). This is because of strong electron withdrawing ability of
rhodanine-3-acetic acid acceptor.26 In the fluorescence emission
spectra, all the synthesized dyes were excited in their absorption
maximum and show the corresponding photoluminescence spec-
tra in the range of 450–560 nm.
In order to understand the feasibility of electron injection from
the excited state of dye molecules to the conduction band of TiO2
and regeneration of dye by the redox electrolyte, electrochemical
measurements were carried out by using cyclic voltammetry
(CV) in DMF medium. The cyclic voltammograms of all the dyes
are shown in Figure S3 (supporting information) and their corre-
sponding data are compiled in Table 1. All the dyes show one irre-
versible peak arising from the oxidation potential around 0.7–0.9 V
which is due to the removal of electron from amine segment of the
dyes and one quasi-reversible peak arising from reduction poten-
tial around 0.9 to 1.8 V which is due to the presence of electron
withdrawing acceptor groups in the dyes. The onset potentials
were determined from the intersection of two tangents drawn at
the rising current and background charging current of the CV trace.
The oxidation potential for the dyes shifts to lower values on
changing the acceptor from rhodanine-3-acetic acid (Al-rh and
Figure 2. Photocurrent–voltage characteristics for the DSSCs based on Al-ma, Al-rh,
Ar-ma and Ar-rh dyes under irradiation (85 mW cm2).
Table 2
DSSC performance parameters of the synthesized dyes.
Dye Jsc (mA cm2) Voc (mV) FF g (%)
Ar-ma 3.48 712 0.57 1.66
Al-ma 2.83 670 0.62 1.38
Ar-rh 2.60 618 0.60 1.12
Al-rh 2.27 529 0.59 0.82
Ar-rh) to acrylic acid (Al-ma and Ar-ma) which may be due to
the stronger electronic communication between the electron rich
amine donor and acrylic acid acceptor. The HOMO energy level
can be calculated from the onset oxidation potential [Eox (onset)]
based on the reference energy level of ferrocene (4.8 eV below
the vacuum level) according to equations mentioned below.
HOMO ¼ ½Eox ðonsetÞ  EFC þ 4:8 eV ð1Þ
LUMO ¼ HOMO  E0—0 ð2Þ
where EFC is the potential of the external standard, the ferrocene/
ferricenium ion (Fc/Fc+) couple. The value of EFC, determined under
the same experimental conditions, was about 0.6 V versus Ag elec-
trode. The excited state (LUMO) of the sensitizer was estimated
from the ground state (HOMO) and E0–0, where E0–0 is the zero–zero
energy of the dyes estimated from the solution absorption edge.27
The calculated LUMO values of all dyes were in the range of
2.81 to 1.96 eV, which is more negative than the conduction
band edge of TiO2 (4.0 eV vs vacuum).28 This suggests that the
effective electron transfer from the excited dye to TiO2 is energeti-
cally feasible. The HOMO values of dyes were in the range of 4.91
to 5.09 eV. This value is more positive than the I =I
3 redox couple
(4.6 eV vs vacuum)29 and so this favours the dye regeneration by
the electrolyte.
To better understand the molecular geometrical structures of
the synthesized dyes, the density functional calculations were car-
ried out by using the B3LYP exchange-correlation functional and
the d-polarized 6-31G (d) basis set implemented in GAUSSIAN 09 pro-
gram.30 The optimized structures and electronic distributions in
the frontier orbitals of the dyes were shown in Figure S4 (support-
ing information). According to the optimized dye structures, the
electron donating amine segment of all dyes exhibits a propeller
form which reduces the aggregation of dye molecules on the
TiO2 surface. The HOMO levels of Al-ma and Ar-ma dyes are mainly
delocalized on the electron donating amine moieties and the p-
spacer phenyl groups, whereas LUMO levels are delocalized
through the p-spacer and acrylic acid acceptor. But in the case of
rhodanine-3-acetic acid acceptor dyes (Al-rh and Ar-rh) the HOMO
and LUMO levels were entirely populated especially on the sulfur
and thiocarbonyl group, and due to the presence of –CH2 group,
the anchoring –COOH group in LUMO level is isolated31 which
may render the anchoring group and the p-spacer in two different
planes. It reveals that the anchoring group must be in conjugation
with the entire dye molecule and the p-spacer should be essen-
tially coplanar with the acceptor group to achieve better electronic
communication. According to the Franck Condon principle, the
overlapping of both HOMO and LUMO levels enhances the elec-
tronic transition between vibrational energy levels32 and this sug-
gests that the dyes (Al-ma and Ar-ma) have strong intramolecular
charge transfer (ICT) nature compared to the dyes (Al-rh and Ar-rh)
which in turn leads to fast electron injection from LUMO level to
TiO2 conduction band upon illumination of light.
In order to test the synthesized dyes as a sensitizer for DSSC
application, the dye-sensitized solar cells were constructed of type
FTO/TiO2/dye/liquid electrolyte/Pt/FTO. The liquid electrolyte is
composed of 0.05 M I2/0.1 M LiI/0.5 M 4-tert-butylpyridine in 2-
methoxypropionitrile solution. The photovoltaic properties of the
Electron lifetime (s/ms) Surface concentration C (mol/cm2) (107)
14.40 1.95
9.04 1.68
3.54 1.35
2.79 0.98
 M. Subbaiah et al. / Tetrahedron Letters 54 (2013) 3132–3136
fabricated solar cells under simulated light irradiation
(85 mW cm2) were shown in Figure 2. The detailed parameters
such as short-circuit current density (Jsc), open-circuit voltage
(Voc), fill factor (FF) and overall conversion efficiency (g) for the
synthesized dyes are summarized in Table 2. Among the four dyes,
Ar-ma sensitized solar cell exhibited a maximum efficiency of
1.66% (Jsc = 3.48 mA/cm2, Voc = 712 mV, FF = 0.57) where in the
case of same dye having cyanoacrylic acid acceptor shows 1.55%
efficiency.33 This is due to the fact that the cyano group in the
acceptor moiety increases the acidity which in turn reduces the
binding ability of the dye on the TiO2 surface.18,19 Under the same
condition, the Al-ma, Ar-rh and Al-rh dyes gave the overall conver-
sion efficiency of 1.38%, 1.12% and 0.82%, respectively. In general,
acrylic acid acceptor dyes (Ar-ma and Al-ma) show high efficiency
than the rhodanine-3-acetic acid acceptor dyes (Ar-rh and Al-rh)
and the observed Voc values are also in the same trend. Upon com-
paring, acrylic acid dyes are giving more number of electrons and
faster electron injection from excited state to TiO2 conduction band
due to the conjugation of anchoring –COOH group with entire dye
molecule and the p-spacer is coplanar with the acceptor group
whereas it was absent in rhodanine-3-acetic acid dyes.34 This is
in accordance with the DFT calculation results mentioned above.
Further, the incident photon-to-current conversion efficiency
(IPCE) (Fig. S5 supporting information) was performed for the fab-
ricated cells. Ar-ma dye-sensitized solar cell shows high IPCE value
of about 25% at 380 nm whereas Al-ma shows 21% at 371 nm, Ar-
rh shows 20% at 477 nm and Al-rh shows 16% at 450 nm. This also
supports that the acrylic acid acceptor dyes are better candidate for
DSSC applications. In order to identify the amount of dye adsorbed
on the TiO2 surface, desorption study was done using 0.1 M NaOH
in ethanol/water (1:1) mixture. The surface concentration (C) of
the sensitizers was spectrophotometrically measured35 and sum-
marized in Table 2. These values indicate that the acrylic acid
acceptor dyes have better adsorption on the TiO2 surface compared
to the rhodanine-3-acetic acid acceptor dyes which again supports
the observed device efficiency and IPCE (%) of the fabricated
devices.
The effect of acceptor moieties in organic dyes for DSSC was fur-
ther elucidated by electrochemical impedance spectroscopy (EIS).
The EIS is a useful technique to understand the important interfa-
cial charge-transfer processes that occur in solar cells, such as the
charge recombination at the TiO2/dye/electrolyte interface, elec-
tron transport in the TiO2 electrode, electron transfer at the coun-
ter electrode and I3 transport in the electrolyte.36,37 The Nyquist
plots and Bode phase plots of fabricated DSSC were displayed in
Figure S6 (supporting information).
In the Nyquist plots, the observed semicircle corresponds to the
charge transfer resistance at the TiO2/dye/electrolyte interface.38
The radius of the semicircles get decreased in the following order
Ar-ma>Al-ma>Ar-rh>Al-rh which indicates that huge charge trans-
fer resistance for Ar-ma dye based DSSC and low charge transfer
resistance for Al-rh dye based DSSC and in turn, this may be
responsible for the achieved device efficiency. Further the electron
recombination life time (s) can be calculated from Bode Phase
plots39 Figure S6 (supporting information) and using the equation
s = 1/xmin, where xmin is the angular frequency. The calculated
electron life time values were listed in Table 2. In the case of
Ar-ma sensitized DSSC, maximum electron lifetime of 14.40 ms
was achieved while comparing with the other sensitizers based
DSSC. This indicates that the Ar-ma based DSSC shows more effec-
tive suppression of injected electrons recombination with the I 3 in
the electrolyte which leads to the enhancement in the photo
voltage, photocurrent and the device efficiency.
In this study, all dyes were synthesized through one-pot Knoe-
venagel condensation reaction. The photophysical, electrochemical
and photovoltaic properties of synthesized metal-free organic dyes
3135
containing diphenylamine and diethylamine donor which is linked
to the acrylic acid and rhodanine-3-acetic acid acceptor through a
phenyl p-spacer were performed. Due to the better binding nature,
the acrylic acid acceptor dye (Ar-ma) shows higher efficiency com-
pared to the same dye having cyano acrylic acid as acceptor instead
of acrylic acid. In general, acrylic acid acceptor based dyes show
higher DSSC performance compared to the rhodanine-3-acetic acid
acceptor based dyes. From the experimental and theoretical re-
sults, we conclude that the anchoring group must be in conjugation
with the entire dye molecule. In addition, the p-spacer should be
essentially coplanar with the acceptor group to (i) make more
cathodic shift in oxidation potential, (ii) reduce the electron recom-
bination at the TiO2/dye/electrolyte interface, and (iii) enhance the
electron life time on the TiO2 conduction band.
Acknowledgments
Authors thank DST, New Delhi (Ref. No. SR/S1/PC-49/2009) and
DST–FIST, New Delhi (SR/FT/CSI-190/2008 dated 16th March 2008)
for the sanction of research fund towards development of new
facilities. Author S.M. thanks UGC, New Delhi for a junior research
fellowship. The author S.A. thanks Department of Science & Tech-
nology for the India–Spain Collaborative Research Grant (DST/
INT/Spain/P-37/11 dated 16th December 2011) to him.
Supplementary data
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.tetlet.2013.04.
012.
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