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Synthesis and characterization of a conjugated

porphyrin dyad entangled with carboxyl
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Cite this: New J. Chem., 2021,

45, 1430 functionalized benzimidazolium: an efficient
metal free sensitizer for DSSCs†
Darpan V. Bhuse and Pundlik R. Bhagat *

As an archetypal functional molecule, porphyrin is the nature’s best photosynthetic pigment in plants,
which mimics the principles of solar energy conversion. Considering the prodigious ability of porphyrin
to harvest light, we present the stepwise synthesis of a novel conjugated meso-substituted porphyrin
dyad entangled with carboxyl functionalized benzimidazolium moieties (CPDCFBM) as a sensitizer for
application in a dye sensitised solar cell (DSSC). 1,4-Di(4-amidostyryl)benzene functionalised with a
benzimidazole moiety served as a spacer between two substituted porphyrin moieties. The dyad was
characterized using analytical techniques such as Fourier-transform infrared spectroscopy, ultraviolet-
visible absorption spectroscopy, nuclear magnetic resonance spectroscopy, thermogravimetric analysis,
BET surface area analysis, cyclic voltammetry (CV) studies and electrochemical impedance spectroscopy
(EIS). The band gap measured using UV-vis spectroscopy was found to be 1.42 eV. The highest occupied
molecular orbital and lowest unoccupied molecular orbital energy levels calculated from CV studies
revealed that the frontier orbital energy levels make the system suitable for use as a sensitizer in
conjugation with TiO2 in DSSCs. A DSSC fabricated using dyad sensitized TiO2 as an iodide tri-iodide
redox couple exhibited a power conversion efficiency of 6.9%, under illumination (AM 1.5, 100 mW cm2)
Received 3rd November 2020, with a sensitization time of 4 h without adding any efficiency booster and anti-aggregating agents. The
Accepted 3rd December 2020 strong tethering of the dyad to the TiO2 surface was achieved via linking through six carboxylate groups to
DOI: 10.1039/d0nj05387b form an envelope around TiO2 to ensure excellent electronic communication and good stability against
the aggregation of the dyad. An EIS study demonstrated that the dyad shows faster electron injection than
rsc.li/njc recombination.

1. Introduction (polypyridyl complexes, viz. N3, N719, and N749) have been used
to achieve lab-scale power conversion efficiencies (PCEs) of up to
Ever increasing energy demands in the context of dwindling 14.3% in DSSCs due to the effective channeling of excitation
fossil fuel reserves is the most important global issue that energy from the Ru metal core to the semiconductor.4 However,
needs to be tackled soon. To this aim, solar energy produced the rarity, high cost, purification difficulty, toxicity of Ru and the
using solar cell technology has emerged as a cheap, efficient, low absorption coefficient of the Ru–dye inhibit the widespread
clean and green alternative to fossil fuels. To harness solar application of these complexes.5,6 Therefore, metal-free organic
energy, four generations of solar cells are available.1 Among dyes with numerous molecular structures featuring a p-bridging
them, organic sensitizer (dye) based solar cells (DSSCs) are quite extension between the donor and acceptor have been screened
popular owing to their easy design and synthesis, tailorable and proposed as viable alternatives to Ru complexes. Using this
absorption profiles and properties, quick junction formation, strategy, an organic, non-porphyrin based thiophene derivative
non-toxicity and low production costs over those of their inorganic dye was shown to achieve a maximum PCE of 7.19%.7
counterparts.2,3 To date, ruthenium-based organic complexes Another class of dyes used in DSSCs is based on the
archetypal functional molecule, porphyrin. This is a natural
Department of Chemistry, School of Advanced Sciences, pigment that can be used to achieve photosynthesis, charge/
Vellore Institute of Technology, Vellore, Tamilnadu – 632014, India.
energy transfer, catalytic conversions, and transport and storage
E-mail: drprbhagat111@gmail.com
† Electronic supplementary information (ESI) available: 1H and 13C NMR and
in plants and animals.8,9 In the natural process of photo-
FT-IR spectra of the intermediates and the final dyad, EDAX of the dyad and the synthesis, porphyrin mimics the principles of solar energy conver-
dyad coated on TiO2 surface. See DOI: 10.1039/d0nj05387b sion and therefore can be evolved as a parallel, smart and green way

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of light harvesting.5,10 A typical porphyrin has a conjugated level of the semiconductor. A selected redox shuttle needs to be
aromatic 18 p electron macrocyclic system formed by the linking matched in energy with the highest occupied molecular orbital
together of four pyrrolic subunits via a methine bridge as an (HOMO) of the dye for the normal working of a DSSC.23 The
active centre with numerous functional molecules attached to common redox couples used in DSSCs are iodide/tri-iodide,
its periphery.11,12 After the pioneering study on b substituted sulfide/polysulfide and an equimolar mixture of Co2+/Co3+,
chlorophyll reported a 2.6% PCE in 1993 for DSSCs,13 numerous Fe2+/Fe3+, Ru2+/Ru3+ complexes.20,24,25 Using a state-of-the-art
research studies have been reported, with a continuous metal-incorporated redox couple in porphyrin based DSSCs,
enhancement made in the PCE achieved by making modifi- encouraging results (up to 13% PCE) have been reported via the
cations to the structure until a 6.0% benchmark efficiency was intentional setting of energy profiles (of the dye and redox
reached, very close to that reported for the ruthenium-based N3 couple) to achieve a higher Voc value.5,20,22,26 Using this strategy, a
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dye in 2009.8,14 Further efforts made on the design and synthesis Fe2+/Fe3+ complex (bipyridyl) exhibiting readily exchangeable
of numerous porphyrin derivatives via the functionalization of ligand platform set a record photovoltage of 1.42 V for a DSSC in
four meso and eight beta positions realized enhanced absorption 2018.27 The state of the electrolyte-containing redox couple, is
ability in terms of the reshuffling of a characteristics Soret band another concern, which largely decides the long-term applicability
(400–500 nm) and several Q-bands (550–750 nm).11 Based on this and stability of the device. The state varies from liquid, quasi-
principle, several research studies were reported in the literature liquid to solid depending upon the state of the solvents/
with PCEs of more than 10% for DSSCs.5,6,12,15–19 Probing additives used. For organic based DSSCs, organic solvents
further to design a porphyrin via the attaching of suitable (acetonitrile, DMSO, MPN) are preferred, however, they often
electron donor (D) and acceptor (A) moieties on opposite sides suffer from leakage and stability issues, so, the use of non-toxic,
of the porphyrin exhibited an important electronic push–pull, as non-flammable aqueous-based electrolyte or electrolytes
first observed in 2009, reported to have an efficiency close to trapped in a solid or quasi-solid matrix (gel/hydrogel) has been
the well-known ruthenium-based dye N719 under similar suggested.28–30 Multi-functional, multi-polymer membranes31
conditions.14 Modification to the periphery of the porphyrin, and a surface-modified photo-polymer electrolyte membrane32
often called D–p–A engineering, provides an effective way to (PEM) with tailored surface characteristics have been demon-
separate the photogenerated excitons before their recombina- strated to be promising solid electrolytes in DSSCs.
tion, and led to a record 12% PCE in 2011 for a zinc-doped The assembly of electrodes is another important component
monomer porphyrin using cobalt-based electrolytes.20 However, of DSSCs. This includes a working photoelectrode (WPE) and a
this type of electronic push–pull mechanism is absent in counter electrode (CE). A WPE is a dye impregnated semi-
inorganic based solar cells, leading to poor PCE performance conductor layer, deposited over a conducting glass plate. Upon
as charge recombination predominates before separation is illumination, the dye molecule excites and injects photo-
achieved.21 Based on the D–p–A framework and Soret band generated charge carriers from the lowest unoccupied molecular
engineering, a Zn-doped porphyrin dye with dialkyl/aryl amines orbital (LUMO) of a dye to the conduction band (CB) of a
as donors and ethynyl benzoic acid as an acceptor set another semiconductor, traveling further to the external circuit via the
benchmark record of a PCE of 13% for DSSCs in 2014 using a conducting base. To compensate for this, the hole in the HOMO
cobalt-complex redox mediator.22 However, the record in of the dye is filled up via the oxidation of a redox species in the
efficiency was set with the use of a special cobalt-based electrolyte, electrolyte. For injection to occur, the energy profile of the
indicating that further efficiency augmentation is based not only semiconductor and the dye should match (ECB o Edye-LUMO).
on the porphyrin engineering but also on advances in the redox A better performing DSSC needs a crystalline, wide band gap
couple.22 Furthermore, with the inherent limitations of the por- semiconductor with a nano/mesoporous surface area to ensure
phyrin to exhibit a relatively low PCE (10–14%) under standard good dye loading and charge transport. The most commonly
conditions, the task of improving the PCE beyond 14% underlines used wide band gap semiconductors are ZnO, NiO, TiO2,
the need for also achieving advances in the other components of BaSnO3, Zn2SnO4 and SrTiO3.33,34 Among them, a Zn2SnO4
the DSSC (viz., counter electrodes and working electrodes).5 based WPE has shown the highest B28% incident photon
There are four important components of a working DSSC, conversion efficiency (IPCE) for DSSCs (not overall efficiency).35
namely, the dye (porphyrin/organic based), the semiconductor Recently, a barium titanate based perovskite material (BaSnO3,
electrode (working photoelectrode, WPE), the counter electrode Eg B 3.2 eV) exhibited 6–7% PCE in a DSSC owing to its high dye
(CE), and the redox couple dissolved in a suitable electrolyte. absorption rate (towards N719), high electron mobility and
The overall efficiency depends on each of these components; the presence of numerous defect sites, which facilitate charge
therefore, they need to be investigated individually before their transfer in DSSCs. However, the persistence of issues such as
combination to evolve an efficient DSSC device. phase purity and incomplete phase conversion limits their
A redox couple constitutes one of the key components of a use.34,36 WPEs based on TiO2 are still preferred owing to their
DSSC that helps to transport photogenerated charge carriers non-toxicity, low cost, ready availability and eco-friendly
across the electrodes. The maximum extractable voltage (Voc) nature.22,33 Another electrode of a DSSC is the counter electrode
from a DSSC greatly depends on the redox potential of the (CE), which assists in the transfer of electrons from the external
redox couple chosen and corresponds to the energy difference circuit back to the redox couple via the electrolyte medium. The
between the redox potential of the redox couple and the Fermi CE is responsible for the regeneration of redox species and the

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completion of the circuit. The most common CE used in DSSCs mechanism between the extensively conjugated spacer (accep-
is platinum, but owing to its scarcity, high cost and lack of tor) and six serving carboxylate moieties is expected to alter the
stability, other materials such as alloys, carbon materials, con- electronic and optical profiles of the dyad besides resulting in
ductive oxides, polymers and transition metal chalcogenides effective charge separation. The strategy to incorporate six
have been developed.37 Among them, a meso/nano-porous carboxylate groups per dyad molecule is expected to provide
organic polymer (PCE – 7%),29 carbon black (PCE – 8.4% with better electronic coupling via six-fold tethering to TiO2, leading
N719)38 and carbon nanotubes (CNTs, PCE – 7.8%)39 have to excellent stability against aggregation. In this article, we
exhibited good and stable PCE performance due to their good emphasize the use of a metal-free porphyrin dyad, TiO2 semi-
electron transfer kinetics and stability compared to those of their conductor, and aqueous iodide–tri-iodide based electrolyte
platinum counterparts.40 Recently, a high performing CE based with no additives to evolve a simple, green, true energy gene-
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on heterogeneous FeNi3/nickel ferrite nanoparticles decorated rator device.

on a graphene network was developed as a stable and low cost,
electrocatalyst CE for organic-based DSSCs, demonstrating a
12.14% PCE versus 8.3% with platinum.41 2. Experimental details
The dye, a basic component of a DSSC, is considered as the 2.1 Materials
‘heart’ of the device, and therefore needs to be carefully
designed for maximum performance. The design and engineering 4-Bromoaniline (99%), sodium chloride (98%), n-hexane and
of porphyrins, in general, involves the following popular stra- chloroacetyl chloride (98%) were acquired from Avra Pvt. Ltd.
tegies: (i) attaching donor or acceptor groups at meso or b Ethanol (99.9%) and hydrochloric acid (35.8–38.0%) were pur-
positions,22,42–44 or attaching spacers such as alkyl chains at the chased from Fischer Scientific. Divinyl benzene was obtained
ends,8,19,45 called Soret band reshuffling (in the absence of an from Merck. Sodium hydride (60% dispersion in paraffin oil),
acceptor molecule, the porphyrin moiety itself behaves as an formaldehyde solution (37–41% w/v AR), sodium hydroxide,
acceptor); (ii) attaching a donor and acceptor to opposite ends salicylaldehyde and pyrrole were purchased from S.D. Fine-
of porphyrins,46 (D–p–A engineering, to allow efficient charge Chem Ltd. Ethyl acetate (99%), chloroform and dimethyl
separation); (iii) metalation of free porphyrin with zinc,47 direct sulfoxide-d6 (deuteration min 99.8% for NMR spectroscopy)
fusion of porphyrins18 or attaching two or more porphyrin rings were obtained from Sisco Research Laboratories Pvt. Ltd.
with appropriate spacer molecules,10,14 or the introduction of Benzimidazole (99%) and tetrahydrofuran (dry) were obtained
a p-extended chromophore (conjugation extension) on the from Spectrochem. N-Methyl-2-pyrrolidone (NMP) (99%) was
porphyrin ring9,10,48,49 (to reshuffle the band gap and to acquired from HIMEDIA. The fluoride-doped tin oxide (FTO)
enhance the absorption profile); (iv) attaching an appropriate films and TiO2 (99.9%) with a particle size of 30–50 nm were
anchoring group at the edge of the dye50,51 (to link the dye with a purchased from Ultra-nanotech, Bangalore. 3-Bromopropionic
semiconductor for electronic communication); (v) modifications acid (97%), tetrabutylammonium hexafluorophosphate (98%),
to the base structure of the porphyrin, e.g. replacement of N by S ferrocene (98%), dimethyl formamide (DMF), and acetonitrile
or linking of the carbon chain to N in the porphyrin core52 (99.8%) were secured from Sigma-Aldrich. The aqueous solutions
(causes subtle changes in the electronic properties of the dye) were prepared in distilled water. All of the chemicals mentioned
and (vi) attaching multiple anchoring groups at the edges of the were used without any purification unless otherwise stated.
dye53–55 (to prevent the aggregation of porphyrin molecules and
quenching of the photovoltaic effect). The ease in design and 2.2 Electrode preparation
engineering, besides other advantages such as non-toxicity, low 2.2.1 Slurry preparation. A slurry of titanium dioxide and
cost, etc., have made this archetypal molecule popular for the CNTs dispersed in NMP solvent was used to obtain the TiO2/
renaissance of third generation solar cells.56,57 FTO and CNT/FTO films respectively. The titanium dioxide and
Although porphyrin exhibits an efficiency of more than 13% CNTs (100 mg each) were dispersed separately in 5 ml of NMP
in DSSCs, the commercialization of devices still needs to solvent under sonication for 30 min.
address related issues such as severe aggregation, long-term 2.2.2 Dyad solution preparation. The dyad solution was
stability, toxicity, volatility and leakage of the solvents and the prepared by sonicating 0.1 M dye in NMP solvent for 1 h.
use of numerous additives (such as hole scavengers, efficiency 2.2.3 Electrodes and film fabrication
enhancers, stabilizing agents, anti-aggregating agents, dopants, 2.2.3.1 Preparation of electrodes for DSSCs. FTO glass slides
etc.). The latter makes the DSSC a ‘chemical generator’ rather (80% transmittance) were used to prepare dyad/TiO2/FTO and
than an ‘electricity generator’.58 CNT/FTO electrodes. The FTO slides were cleaned by sonicating
In view of these issues, we propose a facile synthesis of a them successively in deionised water, ethyl alcohol and acetone
dyad by coupling two porphyrin moieties via 1,4-di(4- each for a period of 30 min. To prepare TiO2/FTO, a cleaned
amidostyryl)benzene functionalized with a benzimidazole glass slide was coated with a slurry of TiO2 using the Doctor
moiety to serve as an electron accepting spacer, while the blade technique59 and subsequently annealed in an oven under
periphery of the porphyrins is entangled at the meso positions vacuum at 200 1C. To prepare a dyad/TiO2/FTO photoanode, a
with carboxyl functionalized benzimidazolium serving as a TiO2/FTO film was sensitized with the dyad by dipping it in a
donor to evolve a D–p–A system. A strong electronic push–pull dyad solution for 4–8 h and subsequently drying it in an oven at

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100 1C for 1 h. Similarly, a cathode electrode was prepared by (CNT/FTO), each with a surface area of 0.5  0.5 cm2 were
coating a cleaned FTO glass slide with a dispersion of CNTs dipped in a 30 ml aqueous solution of electrolyte containing an
followed by the removal of solvent at 200 1C in an oven under aqueous iodide–tri iodide redox shuttle (0.05 M KI, 0.01 M I2) to
vacuum. A 0.5  0.5 cm2 workable area of the photoanode was form a DSSC. The rest of the area of both electrodes was
used for DSSC measurements. masked using M3 adhesive tape. The distance between the
electrodes was kept at B2 cm. The cell was kept in the dark for
2.2.3.2 Preparation of electrodes and electrolytes for cyclic 1 h to establish an equilibrium between the electrodes and
voltammetry (CV) and electrochemical impedance spectroscopy electrolyte before the actual measurements were carried out. All
(EIS). For CV and EIS measurements, a glassy carbon electrode measurements were conducted using a xenon light source with
(GCE) (active area 0.7 cm2) sensitised with the dyad was used. an input power of 100 mW cm2. The source was calibrated
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A layer of dyad was deposited on a clean GCE by dipping it in a using a standard Lux-meter (Meco). An Auto Lab electro-
slurry of dyad in NMP and subsequently drying it at 100 1C in chemical workstation (PGSTAT204) in linear scan mode (LSV)
an oven under vacuum. A platinum wire and a homemade was used to acquire the data. The leads supplied with the
Ag/Ag+ electrode in ethanol were used as counter and reference instrument were used for electrical connection purposes. The
electrodes, respectively. 0.1 M tetrabutylammonium hexafluoro- stability and accuracy of the DSSC were checked by the setting
phosphate (NBu4PF6) in DMF was used as an electrolyte. up of five experimental devices. The efficiency was found to be
All solutions were purged with dry nitrogen (N2) gas before stable (within the experimental error of 1%) for 25 cycles
measurements were carried out. studied at the experimental level (under controlled temperature
of the electrolyte, not exceeding 50 1C).
2.3 Characterization techniques
Nuclear magnetic resonance (NMR) spectra of the dyad were 2.5 Synthesis of dyad-CPDCFBM (3B)
recorded in DMSO-d6 and CDCl3 on a Bruker spectrometer A series of substitution reactions were carried out to obtain
operating at 400 MHz using tetramethylsilane (TMS) as an various intermediate and final products, as displayed in
internal standard. Thermogravimetric analysis (TGA) of the dyad Scheme 1.
was carried out in the range of 30–800 1C at a rate of 10 1C min1 2.5.1 Synthesis of 1,4-phenylene bis(ethene-2,1-diyl)
under a N2 atmosphere on a thermogravimetry/differential dianiline: (1A). Divinyl benzene (DVB) was destabilized by
thermal analysis (TG/DTA) SII thermoanalyzer, 7200 (Seiko, repeated washing with 1% of NaOH followed by water. The
Japan). Fourier-transform infrared (FT-IR) spectra of the dyad, organic layer was separated from the aqueous layer and dried
dyad/TiO2/FTO and CNT/FTO were recorded on a Shimadzu over anhydrous sodium sulphate for 4–5 h. The product (1A)
FT-IR spectrophotometer using the KBr pellet method. Brunauer– was obtained by reacting 4-bromoaniline with DVB in a 2 : 1
Emmett–Teller (BET) surface area measurements were carried out ratio. Typically, carbon–carbon coupling (Heck reaction) of
at 77 K (liquid N2) using a Quanta chrome nova-1000 instrument 4-bromoaniline (13.7 g: 80 mmol) and DVB (5.20 ml; 40 mmol)
analyser. Specific surface area, average pore diameter and pore in ethanol as a solvent was carried out in a 100 ml beaker under
volume were measured from N2 adsorption–desorption isotherms. 5 W light-emitting diode (LED) white light (a source of UV-vis
Before analysis, samples were degassed at 250 1C for 5 h under light) for 24 h at ambient temperature, as described by Bhansali
vacuum for the removal of moisture and unwanted adsorbents. CV et al.60 The obtained red coloured product was shaken in a
and EIS measurements were performed using an Auto-Lab electro- separating funnel with a mixture of ethyl acetate and saturated
chemical workstation (PGSTAT204) in DMF solvent containing solution of NaCl in a 1 : 1 ratio. The product dissolved in the
0.1 M tetrabutylammonium hexafluorophosphate as an electrolyte organic layer leaving behind unreacted reagents in the aqueous
across a potential window of 2.0 to 1.2 V. A three-electrode phase. Traces of water in the organic layer were removed by
configuration consisting of a GCE as the working electrode, Ag/Ag+ adding anhydrous sodium sulphate to it for 3–4 h. Finally, the
(non-aqueous) as a reference electrode and platinum (Pt) wire as sodium sulphate was filtered off and the solvent was evapo-
the counter electrode was used. The scan rates were set as 0.025, rated under vacuum using a rotary evaporator to obtain a red
0.050, 0.1, 0.3, 0.5, 0.7 and 0.9 V s1. Linear scanning voltammetry coloured liquid of 1A (10 ml, 44%).
(LSV) was used to investigate the photoelectrochemical perfor- 1
H NMR (400 MHz, DMSO-d6): d 7.54 (s, 4H), 7.42 (s, 4H),
mance of the DSSC. The surface morphology and compositional 7.15 (d, 4H, J = 8.41 Hz), 6.58 (d, 4H, J = 8.37 Hz), 5.28 (s, 4H)
analysis of the electrode materials used for the DSSC were [see Fig. S1 in the ESI†].
investigated using a scanning electron microscope (SEM, Carl 13
C NMR (100 MHz, DMSO-d6): 148.45, 136.68, 129.17,
Zeiss EVO-18) equipped with an energy dispersive X-ray (EDAX) 128.87, 127.75, 123.84, 114.69 [see Fig. S2 in the ESI†].
spectrometer. The data measurements were performed within the 2.5.2 Synthesis of 1,4-phenylenebis(ethene-2,1-diyl)bis(4,1-
instrumental error limits of the respective instruments. phenylene)bis(2-chloroacetamide): (1B). The second step
involved the functionalization of 1A with chloroacetyl chloride
2.4 DSSC device fabrication and methodology to produce the intermediate 1B. In a 50 ml round-bottom flask,
A special homemade square cell with dimensions of 3 cm (l)  2 g of NaOH was dissolved in an adequate quantity of water. To
3 cm (b)  4 cm (h) with a flat surface was used to make a DSSC this clear solution, 1A (10 g; 22 mmol) was added and stirred
device. The photoanode (dyad/TiO2/FTO) and the cathode magnetically to obtain a homogenous suspension. The flask

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Scheme 1 Scheme of the reactions exhibiting the stepwise synthesis of the CPDCFBM dyad.

was then placed in a freezing mixture (ice and salt) and after 200 ml conc. HCl solution, taken up in a 500 ml round-bottom
keeping it at low temperature, chloroacetyl chloride (4.95 g; flask was stirred for 5 min in an ice bath. To this, 37%
44 mmol) was added dropwise, carefully in such a way that the formaldehyde (36 ml, 402.1 mmol) was added dropwise with
temperature did not exceed 5 1C. After complete addition, the stirring. The stirring was then continued for a further 10
magnetic stirring of the reaction mixture was continued for 44– minutes. Finally, salicylaldehyde (30 ml, 288 mmol) was added
48 h.61 Finally, the sticky green coloured product was washed with continuous stirring. After 48 h, the excess acid from the
repeatedly with distilled water to remove unreacted reactants product was removed by washing it with water using a decanta-
and dried in an oven at 110 1C for 2–3 h. The product was tion technique.62 The product was recrystallized from n-hexane
recrystallized using ethanol to get obtain 1B (6 g, 52%). solvent to obtained a white solid of 2A (9 g 44%).
1 1
H NMR (400 MHz, DMSO-d6): d 10.44 (s, 2H) 7.57 (q, 16H, H NMR (400 MHz, DMSO-d6): d 10.92 (s, 1H), 10.27 (s, 1H),
J = 8.71 Hz), 4.32 (s, 4H) [see Fig. S3 in the ESI†]. 7.71 (s, 1H). 7.27 (d, 1H, J = 1.95 Hz), 7.58 (dd,1H, J = 8.95, 2.30),
13
C NMR (100 MHz, DMSO-d6): 165.33, 138.23, 132.16, 7.03 (d, 1H, J = 8.48 Hz), 4.75 (s, 2H) [see Fig. S5 in the ESI†].
13
121.82, 116.03 [see Fig. S4 in the ESI†]. C NMR (100 MHz, DMSO-d6): 191.19, 161.20, 137.43,
FT-IR (KBr, n/cm1): 3261, 3194, 3124, 3076, 1668, 1606, 129.59, 129.27, 122.64, 118.22, 46.18 [see Fig. S6 in the ESI†].
1544, 1485, 1394, 1336, 12880, 1246, 1188, 1070, 1008, 962, 860, 2.5.4 Synthesis of 5-((1H-benzoimidazole-1-yl)methyl)-2-
819, 769, 734, 567, 497 (Fig. 1a, black spectrum). hydroxybenzaldehyde: (2B). A 60% dispersion of sodium
2.5.3 Synthesis of 5-(chloromethyl)-2-hydroxy benzaldehyde: hydride in paraffin oil, (2.64 g; 110 mmol) was mixed under
(2A). A chloromethylated salicylaldehyde intermediate (2A) stirring with n-hexane in a 250 ml two-neck round-bottom flask.
was prepared by reacting salicylaldehyde with formaldehyde. A The paraffin oil dissolved in n-hexane was removed via

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Fig. 1 (a) FT-IR spectrum of intermediates 3A and 1B, (b) FT-IR spectrum of CPDCFBM, (c) thermogravimetric analysis of CPDCFBM, (d) pore volume of
CPDCFBM, and (e) pore diameter of CPDCFBM.

1
decantation and finally, any traces of n-hexane were removed H NMR (400 MHz, DMSO-d6): d 10.19 (s, 2H), 9.77 (s, 1H),
via air drying. To this, benzimidazole (13.8 g; 118 mmol), 8.16 (s, 1H), 8.05 (d, 2H, J = 8.13Hz), 7.82 (s, 1H), 7.64 (s, 3H),
dissolved in 40 ml of THF was added slowly. After addition, 7.01 (d, 2H, J = 8.13 Hz), 5.66 (s, 2H), 4.67 (s, 2H), 2.98 (s, 2H)
the flask fitted with a condenser was heated in an oil bath at [see Fig. S9 in the ESI†].
13
60 1C under continuous stirring. After around 2 h, 2A (20 g; C NMR (100 MHz, DMSO-d6): 191.80, 172.38, 161.32,
118 mmol), dissolved in 40 ml of THF was charged slowly into 143.03, 136.92, 131.62, 131.57, 131.00, 129.69, 129.90, 127.35,
the reaction mixture under reflux conditions. After 44–48 h, a 127.28, 125.08, 122.74, 118.49, 114.26, 114.17, 79.33, 49.63,
dark brown viscous product was obtained by evaporating the 43.16, 33.03 [see Fig. S10 in the ESI†].
THF solvent from the organic layer using a rotary evaporator. 2.5.6 Synthesis of 1,1-((((1,4-phenylenebis(ethene-2,1-diyl))
The crude product was shaken with a mixture of ethyl acetate bis(4,1-phenylene))bis(azane-diyl))bis(2-oxoethane-2,1-diyl))bis
and brine solution in a separating funnel to separate the (3-(3-formyl-4-hydroxybenzyl)-1H-benzoimidazol-3-ium): (3A).
unreacted reactants from the product. The separated organic The extended p conjugated intermediate compound 3A, the
layer was dried over anhydrous sodium sulphate for 3–4 h, and main linker of the proposed dyad 3B, was obtained by coupling
the solvent was then evaporated to obtain the product.63 This 1B with 2B in a 1 : 2 ratio. In a typical reaction, 1B (9.3 g,
product was then further washed with diethyl ether under 20 mmol) and 2B (10 g, 40 mmol) were taken up in a 100 ml
magnetic stirring for 2–4 h to obtain a fine yellowish powder round-bottom flask. To this, 50 ml of chloroform was added
of 2B (14 g, 44%). and the solution was refluxed at 60 1C. After 44–48 h, the
1
H NMR (400 MHz, DMSO-d6): d 10.78 (s, 1H), 10.22 (s, 1H), obtained product was filtered using Whatman filter paper,
8.40 (s, 1H), 7.63 (s, 2H), 7.51 (s, 2H), 7.19 (s, 3H), 6.97 (d, 1H, washed with chloroform and finally dried in air to obtain a
J = 8.35Hz), 5.44 (s, 1H) [see Fig. S7 in the ESI†]. light green coloured solid product65 of 3A (7 g, 41%).
13 1
C NMR (100 MHz, DMSO-d6): 191.25, 160.82, 144.58, H NMR (400 MHz, DMSO-d6):d 11.02 (s, 2H), 10.24 (s, 2H),
144.05, 136.11, 133.98, 128.47, 128.05, 122.89, 122.67, 122.07, 9.82 (s, 2H), 8.23 (s, 4H),8.01 (s, 5H), 7.86 (s, 4H), 7.68 (s, 13H),
119.96, 118.19, 111.15, 47.23 [see Fig. S8 in the ESI†]. 7.56 (s, 3H), 7.07 (d, 3H, J = 7.97 Hz), 5.75 (s, 4H), 5.61 (s, 4H)
2.5.5 Synthesis of 3-(-2-carboxyethyl)-1-(-3-formyl-4-hydroxy- [see Fig. S11 in the ESI†].
13
benzyl)-1H-benzoimidazole-3-ium: (2C). This step involves the C NMR (100 MHz, DMSO-d6): 191.11, 164.09, 163.97, 161.59,
functionalization of the benzimidazole nitrogen with 3-bromo- 145.05, 143.86, 138.01, 137.06, 132.43, 132.24, 131.80, 130.84, 129.65,
propionic acid to obtain 2C. In this reaction, 2B (13 g, 51.6 mmol) 127.49, 127.38, 127.28, 126.34, 124.93, 122.99, 121.78, 118.62, 116.18,
was dissolved in 40 ml of chloroform in a 100 ml round-bottom 114.95, 114.21, 49.63, 31.12 [see Fig. S12 in the ESI†].
flask, and to this, 3-bromopropionic acid (7.84 g, 51.6 mmol) was FT-IR (KBr, n/cm1): 3041, 2989, 2892, 2834, 1687, 1660,
added and the mixture was refluxed at 60 1C. After 44–48 h, a 1609, 1547, 1487, 1397, 1351, 1284, 1252, 1201, 1149, 1071,
viscous yellow liquid product was obtained by evaporating the 1008, 824, 748, 705, 602, 558, 496, 424 [see Fig. S13 in the ESI†].
solvent from the reaction mixture using a rotary evaporator64 2.5.7 Synthesis of dyad CPDCFBM: (3B). 2C (2.1 g;
(3.7 g, 22%). 6.6 mmol), 3A (1 g; 1.1 mmol) and pyrrole (0.6 g; 8.8 mmol)

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in a 6 : 1 : 8 ratio were mixed with glacial acetic acid and The nature of the N2 adsorption–desorption isotherm is clearly
sonicated for 15–20 minutes to obtain a homogenous suspen- recognized to be type II (or type IV), suggesting the mesoporous
sion. The suspension was then refluxed in a 100 ml round- pore texture of the dyad (3B). The analysis gave a pore size of
bottom flask for 40 minutes at 80 1C.66 The purple coloured 0.713 nm and a high surface area of 500.335 cc g1 with a pore
solid obtained was then washed with water several times under volume of 1.045 cc g1.
suction and finally rinsed with acetone and dried at 60 1C
under vacuum overnight to obtain 3B 1 g, 27%. 3.2 UV-vis studies
1
H NMR (400 MHz, DMSO-d6):d 10.91 (s, 1H), 10.83 (s, 1H),
The UV-vis absorption spectrum of porphyrin exhibits several
10.23 (s, 2H), 9.85 (s, 5H), 8.28 (s, 3H), 8.00 (s, 12H), 7.9 (s, 44H),
characteristic, recognizable transitions comprising Q bands in
7.46 (d, 3H, J = 7.73 Hz), 7.07 (d, 25H, J = 7.09 Hz), 6.82
the visible region (490–650 nm), Soret or B bands in the near-
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(s, 12H), 6.53 (s, 3H), 5.79 (s, 3H), 5.55 (s, 16H), 4.76 (s, 5H),
UV (400–436 nm) and N, L and M bands in the deep UV regions
2.98 (s, 20H), 1.94 (s, 1H), 1.25 (s, 2H), -0.12 (s, 4H) [see Fig. S14
(200–350 nm). Metal-free porphyrin shows four Q (I, II, III, IV)
in the ESI†].
bands while a metallised porphyrin exhibits only two Q (a,b)
bands. The Q bands are considered as being the most sensitive
bands to the environment of the porphyrin.68 A typical proto-
3 Results and discussion porphyrin exhibits moderate intensity Q bands at 506, 541, 576
3.1 Dyad (CPDCFBM, 3B) characterization and 605 nm and a strong, narrow B band at around 400 nm.
Fig. 2(a) displays the UV-vis spectrum of the designed dyad. It
The as-prepared dyad has a carboxylate tethered substituted
shows the presence of four broad Q bands and a strong Soret
benzimidazole moiety attached at the meso position of both the
band. The peaks that can be identified as medium intensity Q
porphyrins at three sites, while the extended p conjugated
bands are at 427, 519, 833, and 855 nm and there is also a
spacer (3A) joins both porphyrin moieties at the remaining
strong Soret band. The broadening of the Q bands indicates
meso position. The FT-IR spectra of the intermediate 1B (black)
strong electronic coupling between the two porphyrin rings in
and 3A (red) are shown in Fig. 1(a). The FT-IR spectrum of 1B
the dyad via the linker.5 The strong red shifting of the Q bands
shows a broad band between 3200 and 3300 cm1 corres-
and strong blue shifting of the Soret band (B150 nm) can be
ponding to stretching vibrations of the amino groups. The
observed. The bathochromic shifting of the Q bands is due to
peak at 740 cm1 represents a characteristic C–Cl stretching
the basic nature of the benzimidazole moiety, which easily
frequency. The formation of 3A from 1B was confirmed by the
donates non-bonding electrons present on the N atom,
disappearance of the C–Cl band in the FT-IR spectrum of 3A,
thus requiring less energy for transitions to occur.69 The
indicating the conversion of C–Cl to a C–N bond. The incor-
p-conjugation and dimerization on the dyad also helps to change
poration of a hydroxyl group in 3A results in the introduction of
the electron density distribution on the porphyrin, decreasing
a broad peak in the region of 3100 to 3400 cm1 along with
the HOMO–LUMO gap.56,70,71 Fig. 2(b) shows a normalised low
peaks due to aromatic aldehydes in the 1400 to 1600 cm1
energy band to calculate the E0–0 energy (band gap). Steady-state
range, indicating the entwining of benzimidazole with salicy-
absorption spectroscopy was used to calculate the energy of the
laldehyde. The FT-IR spectrum of CPDCFBM (3B) is shown in
band gap. According to the measurements, the dependence of
Fig. 1(b). It exhibits a characteristic band at 1692 cm1 due to
the absorption coefficient near the absorption edge on the
carboxylic groups located at the periphery of the porphyrin
photon energy is given by the equation:72
dimer.67 A broad peak in the range of 3200 to 3500 cm1 can be
assigned to the stretching of amino (N–H) and hydroxyl (–OH) (ahn) = (hn  Eg)n (1)
groups. The bands at 1258 (C–N) and 1395 cm1 correspond to
N–H and CQN, confirming the formation of CPDCFBM (3B) where a is the absorption coefficient of the absorbing material,
[see Fig. S15 in the ESI†]. I0 and It are the intensities of the incident and transmitted
The thermal stability of the dyad was explored via TGA light, respectively, hn is the photon energy, Eg is the band gap of
analysis. Fig. 1(c) displays a thermogram of the dyad. An initial the material and n depends upon the types of transition
6.59% weight loss can be observed in the thermogram, involved. It takes a value of 12 for a direct allowed type band
which begins at 101 1C, attributed to the loss of physiosorbed gap and 2 for indirect allowed (transition). The direct bandgap
moisture from the dyad. The desorbed dyad shows thermal is estimated from the extrapolation of the linearity (after
stability up to 205 1C, thereafter, it rapidly decomposes up to divergence) of the (ahn)2 vs. (hn) plot to the x-axis (Fig. 2(c)).
500 1C, registering a total weight loss of 47.55%. This loss can The gap was estimated as 1.42 eV, which is lower than that of
be ascribed to the degradation of the benzimidazole moiety. free porphyrin (B2.0 eV) due to the strong bathochromic shift,
Beyond 500 1C, a continuous but slow loss up to 800 1C is as expected. In the case of porphyrin, zero-zero energy (E0–0)
observed, accounting for the systematic degradation of remaining between the ground and the excited electronic state in the
porphyrin moieties. lowest vibrational level corresponds to a band gap (Eg). A
The surface area and pore size analysis of 3B was performed similar type of band gap lowering (1.16 eV) was observed by
using BET theory, and Fig. 1(d and e) show the N2 adsorption– Zhang et al. due to the extensive conjugation via a naphtho-
desorption isotherm and pore size distribution, respectively. quinodimethane bridge between porphyrin dimers.71

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Fig. 3 FT-IR spectra of the bare dyad (red) and dyad coated on the TiO2
surface (black).

binding and electronic coupling of the dyad to the TiO2 surface

through carboxylate groups.67

3.4 CV studies
CV is a popular method for estimating the standard electro-
chemical redox potentials (E0) of the molecular species. A
strong correlation of E0 with the energy levels of frontier
orbitals (HOMO, LUMO) and the band edge defines the invalu-
able importance of CV for electronic characterization of
molecules.73,74 The half-wave potentials (E1/2) are the preferred
representation for E0 for the reversible reduction and oxidation
processes. The usual way to obtain E0 is to take average between
the anodic (Ea) and the cathodic (Ec) peak potentials from
voltammograms manifesting reversibility. However, a more
accurate method involves the use of inflection potentials (Eia
and Eic) instead of half-wave peak potentials. This method is
applicable for estimating E0 for irreversible/semi-reversible/
quasi-irreversible (i.e., chemically reversible but electro-
chemically irreversible) and oxidation/reduction processes
exhibiting a slower rate of interfacial electron transfer than
Fig. 2 (a) UV-VIS spectra of the dyad, and (b) normalised low energy Q mass transport.74 We adopted this method to estimate E0 for
band and a plot of (ahn)2 vs. (hn) for calculation of the band gap (Eg). the oxidation and reduction processes. The CV measurements
were performed in DMF solution containing 0.1 mol L1
tetrabutylammonium hexafluorophosphate (NBu4PF6) using a
3.3 Characterization of the photoelectrode dyad-GCE as a working electrode, Pt wire as a counter electrode
The FT-IR spectra of the pure dyad and dyad adsorbed onto the and Ag/Ag+ (in ethanol) as a reference electrode. A ferrocene/
TiO2 surface are displayed in Fig. 3, recorded in order to ferrocenium (Fc/Fc+) redox couple was used as an internal
establish the anchoring ability of the dyad to TiO2. The FT-IR standard. The standard redox potential of Fc/Fc+ was calculated
spectrum of the dyad (Fig. 3, black) exhibits a characteristic at +87 mV using a Ag/Ag+ (0.01 M AgNO3) electrode in DMF
absorption band at around 1694 cm1, which corresponds to containing 0.1 M NBu4PF6 electrolyte.75 Fig. 4 shows the
the n(CQO) stretching vibration of the carboxylic acid group. In voltammograms of the dyad measured at different scan rates
the FT-IR spectrum of dyad/TiO2 (Fig. 3, black), the absorption (0.025 to 0.9 V s1) in the potential window of 2.75 to 1.0 V
band due to n(CQO) has completely disappeared, whereas a at 25 1C under the purging of N2 gas. The voltammogram
significant increase in intensity is observed for the symmetric exhibits two anodic peaks (positive voltage), the first peak
nsym(COO–) and asymmetric nasym(COO–) stretching frequen- corresponding to the oxidation of ferrocene and the second
cies of the carboxylate group at 1406 and 1642 cm1, respec- peak due to the slow oxidation of porphyrin moieties. The
tively. The disappearance of n(CQO) and the increased second peak exhibited its reversibility only at higher scan rates
intensity of nsym(COO–) and nasym(COO–) indicates that a proton (300–900 mV s1) as the electron transfer kinetics match the
is detached from the carboxylic acid group during the adsorp- higher scanning rate. The negative side (negative voltage) of the
tion of the porphyrin onto the TiO2 surface, leading to strong voltammogram clearly displays three reversible cathodic peaks.

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suggests strong electronic coupling between the two porphyrin

moieties via the extensive conjugation between them, giving a
good HOMO level corresponding to the single ground states of
the dyads.77 The difference in the HOMO and LUMO gaps
calculated from CV measurements corresponds to the band
gap of the dye. This value (1.71 eV) is somewhat higher than the
E0–0 energy gap (1.42 eV) calculated from the UV-vis absorption
spectra. This deviation possibly occurs due to the presence of
multiple excited states in the organic molecules.78 Table 1
displays the data obtained from CV curves and those calculated
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from the UV-vis spectrum along with the calculated electron

injection and regeneration energies.

Fig. 4 CVs of the dyad in DMSO solvent, taken at different scan rates from 3.5 SEM characterization of the electrode
0.025 to 0.9 V using a three-electrode system. The surface morphology and composition of the dyad/TiO2/FTO
and CNT/FTO were obtained using a SEM instrument attached
to an EDAX probe. Fig. 5(a) depicts the SEM of the TiO2/FTO
The first peak corresponds to the reduction of ferrocene, the film. An aggregation of spherical nanoparticles producing
other two peaks correspond to the stepwise reduction of the colloids of around 300 nm in size can be clearly observed. This
di-cationic porphyrin moieties in the dyad. A small peak is often called a mesoporous morphology, which is highly
observed at low scan rates (at B0.75 V) may be attributed to desirable for efficient dye absorption and enhancing photo-
the feeble reduction of the benzimidazole moieties, this peak, chemical reactions. Fig. 5(b) shows a SEM image of the TiO2/
however, disappears at a higher scan rate. A similar peak at a FTO surface coated with the dyad, obtained via dip coating. The
potential of 0.1 V exhibits a high peak-to-peak separation due process involves dipping the TiO2 in a dyad colloidal solution
to unknown impurities. The quasi reversible oxidation wave for 4 h followed by solvent evaporation and annealing. The
exhibits an inflection potential of 0.56 V (vs. Ag/Ag+) corres- dyad/TiO2/FTO SEM image clearly exhibits an almost similar
ponding to ground-state oxidation potentials (+0.858 V vs. type of mesoporous morphology to that of bare TiO2/FTO,
saturated calomel electrode, SCE) and represents the HOMO except for an increase in the colloidal size. This is expected as
levels of the dyad. The first irreversible reduction wave of the the dyad forms a uniform sheath over the TiO2 surface via
dyad exhibits an inflection potential of 1.22 V vs. Ag/Ag+ strong bonding between multiple carboxylic acid groups with
(0.922 V vs. SCE), corresponding to the excited state the TiO2 mesoporous surface,67 leading to a non-planar
(reduction) potential and represents the LUMO energy of the covering of the dyad over TiO2. This leads to an increase in
dyad. The second irreversible reduction potential involves the size of the crystallites as observed. The strong linking of the
the reduction of a mono anion to obtain a dyad. The energies dyad with TiO2 helps to prevent dyad aggregation, which
of the LUMO and HOMO levels (vs. SCE) can be calculated otherwise hampers the long term applicability of a DSSC.79
using the empirical equations:76 The EDAX of the bare dyad [see Fig. S16 in the ESI†] exhibits
peaks corresponding to C, N and O, while the dyad coated on
EHOMO = [E1ox vs. ferrocene + 4.988] eV (2) the TiO2 surface [see Fig. S17 in the ESI†] displays the peaks
related to Ti, O and C only, indicating the formation of a dyad
ELUMO = [E1red vs. ferrocene + 4.988] eV (3)
layer on the TiO2 surface (the N peaks are not observable due to
where Eox and Ered are the first oxidation potential and the first relatively low concentration). Fig. 5(c) displays the surface
reduction potential of the dyad respectively, and 4.988 eV is morphology of the counter electrode used. CNTs with an
the reference value of the Fc/Fc+ redox potential. Accordingly, average size of 40 nm and length of around 400 to 450 nm,
the HOMO and LUMO of the porphyrin dimer were calculated composed in a bunch and dispersed on the FTO surface, were
as 5.841 and 4.066 eV (vs. SCE), respectively. The exhibition observed. The film texture is highly porous, exhibiting a high
of a single quasi reversible oxidation potential (positive voltage) surface area upon which to execute counter reactions promptly.

Table 1 Electrochemical data and calculated HOMO and LUMO energy levels, band gaps, and DG values for the electron injection and regeneration
processes. Data used: conduction band energy of TiO2 = 0.750 V (vs. SCE), redox potential of the I/I3 electrolyte = 0.160 V (vs. SCE)

E1ox a [V] E1red a [V] DGinj [V] DGreg [V] HOMOb [eV] LUMOb [eV] Band gap (from UV-VIS) E(0–0) b [eV] Band gap (from CV) [eV]

0.858 0.922 0.172 0.698 5.841 4.066 1.42 1.71

E1ox– observed first oxidation potential. E1red
– observed first reduction potential. DGinj – energy for electron injection from the LUMO of the dyad
to the CB of TiO2. DGreg – energy for regeneration of the dyad radical cations by the I/I3 redox couple. a All potentials are peak inflection
potentials converted to SCE (+0.298 V). b HOMO and LUMO energy levels were calculated using eqn (2) and (3), measured with reference to the
redox potential of the ferrocenium couple, 4.988 eV.

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Fig. 6 Schematic representation exhibiting the important processes of a

DSSC marked with the potential scale vs. SCE (on the right side).

4-tert-butylpyridine, etc., have been used in almost all literature

as efficiency boosters, that work via the shuffling of Fermi levels
or assist to scavenge holes rapidly. Chenodeoxycholic acid,
CDCA, is often used as an aggregation inhibitor. All these
additives, however, make the DSSC unlikely to be stable over
time, because of the various oxidation processes involving
them, distracting the purpose of the ‘electricity generator’
towards a ‘chemical generator’.58
The measurements were performed on five similar DSSC
devices. All of them exhibited a PCE in the range of 6.78 to
7.01%, with an average of 6.9%. The observed variations are
probably due to uncertainties in exposing the exact 0.25 cm2
area of the photoanode to illumination. Fig. 7 shows the IV data
obtained for a fabricated DSSC.
The IV curve (Fig. 7) displays the open circuit photovoltage,
0.610 V (Voc), and the short circuit current density, 14.8 mA cm2
( Jsc), furnishing a maximum obtainable power of 0.0069 W
(under the square) and a fill factor (FF) of 0.76. The conversion
efficiency of the DSSC device was calculated as 6.9%. We
observed a diminishing in the PCE by around 10% with the
Fig. 5 SEM images with scale marks for (a) the bare TiO2 film, (b) dyad
deposited over the TiO2 film, and (c) CNT deposited over the TiO2 anode film. heating up of the electrolyte solution to 50–55 1C due to
prolonged irradiation (heating effect). At this stage, cooling of
the device to room temperature was found to regain the same
PCE reversibly without any notable change in the successive
3.6 Photoelectrochemical studies
A schematic of the processes involved during the working of a
DSSC device is displayed in Fig. 6. A dye is a crucial part of the
DSSC device. A chosen dye must have optimal band gap (B1.2
to 1.8 eV – to absorb maximum a maximum amount of solar
energy), a higher frontier orbital (LUMO) energy than the
conduction band energy of the semiconductor (ECB o Edye-
LUMO) (to inject the excited charges easily) and a lower HOMO
energy of the dye than the redox potential of the redox couple
(Eredox 4 Edye-HOMO) (for quick regeneration of redox couple) to
function as an energy generator.1
The photovoltaic properties of the metal-free dyad on the
TiO2 surface were evaluated under 100 mW cm2 illumination
in 0.05 M KI, 0.01 M I2 electrolyte using an Auto Lab electro-
chemical workstation (PGSTAT204). We performed the mea-
surements using a well-behaved redox system containing no Fig. 7 Current–voltage (CV) plot of the DSSC in iodine electrolyte under
additives. So far, additives such as guanidinium thiocyanate, 100 mW cm2 illumination.

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25 cycles studied, indicating the appreciable stability of the dyad 6.9%, for example, a 1,3,5-triazine bridged Zn-doped porphyrin
and also that of the photoelectrode. However, the heating effects dimer (5.28%),67 an acetylene bridged Zn doped-porphyrin
beyond 80 1C lead to a more than 50% loss in the PCE, probably dimer with multiple electron donating groups (6.21%),42
due to un-estimated deteriorations in the electrolyte or electrode meso–meso directly linked Zn-doped porphyrin dimers tethered
surfaces. at b positions with 2-propenoic/2,4-pentadienoic acids and
To assess the stability of the dyad against aggregation, we polyethylene glycol (4.2%),80 a Zn-doped meso–meso directly
performed DSSC measurements on the dyad for different linked porphyrin dimer based on a double D–p–A sensitizer
sensitization times (4, 8, and 10 h). The data shows no (5.33%)81 and a Zn-doped porphyrin trimer linked with acety-
appreciable variations (42%) in the DSSC performance, indi- lene at the meso position (4.17%).82 However, a few reports exist
cating good stability of the dyad against aggregation.48 The on Zn-doped porphyrin dyads reporting PCEs of B10%,
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annealing of the dyad electrode was observed to be crucial in wherein, the long-lived singlet excited state exists and fast
obtaining a stable PCE. The annealed dyad exhibits much injection dynamics lead to high PCEs.49,77 These dyes set
better and stable performance than the unannealed dyad. The excellent examples of Soret band and D–p–A porphyrin
lowering of the performance may be attributed to poor electro- engineering.16
nic linking of the dyad to the TiO2 surface. The annealing Table 2 displays a summary of the reported performance of
ensures firm chemisorption of the dyad via strong carboxylate DSSCs employing dimer sensitizers with our metal free dyad.
bonding, in addition to hydrogen bonding, leading to better Herein, the data on undoped/doped type dimers are compared
electronic coupling between the dye and the semiconductor. with our dyad concerning doping, dimer attachments, number
The synthesized metal-free dyad exhibited an encouraging of functional/anchoring groups present, set experimental para-
PCE of 6.9% and better stability against aggregation in a true meters including additives used, and the obtained result.
energy generating DSSC (without any additives). After careful The Voc (0.610 V) value obtained for the dyad was found to be
searching of the literature, we found no exact match for the commensurate with the theoretical value, which is the differ-
dyad we synthesized to compare with. Although a huge amount ence in energy between the quasi Fermi energy level of TiO2
of literature is available on monomeric, zinc-doped porphyrin (0.450 V SCE) and the Nernst redox potential of the redox
dyes, only a few reports are available for metal-free dimeric couple (0.160 V vs. SCE). Other key energy parameters, such as
versions. A similar type of metal-free dimer, available in the charge injection energy (DGinj) and dye regeneration energy
literature was reported to have a PCE of 2.86% for a conjugated (DGreg) have been calculated to ensure feasibility of the impor-
meso Schiff-base substituted metal-free porphyrin with thienyl tant processes in DSSCs. DGinj corresponds to the energy
or p-methylphenyl functional groups.10 Some of Zn-doped difference between the LUMO of the dyad (0.922 V vs. SCE)
dimers have been reported to have efficiencies of lower than and the CB of the TiO2 (0.750 V vs. SCE), estimated as

Table 2 Summary of the reported performances of DSSCs employing dimer sensitizers

No. of lin- Redox Dye

Type of Electrode Spacer (with linking kers couple and Additive (if sensitization PCE
Sr. dimer (WPE and CE) position) Donor group/s (anchors) solvent any) time (h) (%) Ref.
1 Metal free TiO2 and 1,4-Di(4- Benzimidazole sub- 6 (carboxyl) I–I3, AQ None 4 6.90 This
CNTs amidostyryl)benzene stituted carboxyl work
(meta–meta)
2 Metal free TiO2 and Pt Schiff base (–CQN–) Thienyl (3)/p-ethylphenyl Nil I–I3, NAQ CDCA, 2 2.86 10
(meso–meso) (3) and phenyl (3) DMPII, TBP
 
3 Zn-doped TiO2 and Pt Substituted benzene Substituted carboxyl (1), 1 (carboxyl) I –I3 , NAQ DMPII, TBP 2 3.80 47
(meta–meta) substituted benzene (6)
4 Zn-doped TiO2 and Pt Nil Aryl (4), polyethylene 2 (carboxyl) I–I3, NAQ* BMII, TBP 12 4.20 80
glycol (2) and propionic/
pentadienoic acid (2)
5 Zn-doped TiO2 and Pt Acetylene (meso–meso) Substituted carboxyl (1), 1 (carboxyl) I–I3, NAQ* CDCA,TBP 1–2 10.40 49
(co- alkyl aryl amine (1), DPMII and
sensitized) substituted benzene (4) cosensitizera
 
6 Zn-doped TiO2 and Pt Pipyridine/glycine Carboxyl (1), substituted 2 (carboxyl I –I3 , NAQ* DMPII, TBP 12 5.28 67
functionalized tria- aryl (2), aryl (3) and pipyr-
zine moiety pipyridine/glycine(1) idine/
glycine)
7 Zn-doped TiO2 and Pt Nil Benzene substituted 2 (carboxyl) I–I3, NAQ DMPII, TBP 12 5.33 81
carboxyl (2), phenyl (2)
and triaryl amine (2)
8 Zn-doped TiO2 & Pt Acetylene (meso–meso) Carboxyl (1), diaryl amine 1 (carboxyl) I–I3, NAQ* CDCA, MPII, 3 6.21 42
(2), phenylamine (1), TBP
substituted benzene (2)
NAQ – non aqueous solvent – acetonitrile (* indicated mixture of acetonitrile and butyl cyanide). AQ – aqueous solvent (water), DMPII – 1,2-
dimethyl-3-propylimidazolium iodide, TBP – 4-tert-butylpyridine, BMII – 3-butyl-1-methylimidazolium iodide, DCA – deoxycholic acid, CDCA –
chenodeoxycholic acid. a A mixture of dimer with co-sensitizer (a monomer porphyrin) was used.

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0.172 V. A more negative value obtained acts as a driving force

for injection of the electrons from the dye molecule to the
semiconductor. Similarly, DGreg, corresponds to the difference
between the HOMO energy of the dyad (+0.858 V vs. SCE) and
the redox potential of the redox couple (+0.160 V vs. SCE),
estimated as +0.698 V (vs. SCE). A positive value obtained
ensures the effective regeneration of the dye molecules in the
DSSC. The driving energy parameters, which favour the impor-
tant thermodynamic processes in DSSCs, are exhibited in
Table 1 and are also scaled on the right hand side of Fig. 6
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for easy reference.

DSSCs based on monomer porphyrins set a record PCE of
B13%, their commercialization however, needs further addres-
sing of the issues related to stability against aggregation and ill
effects of the numerous additives. Although we got an encoura-
ging PCE of B7% and excellent anti-aggregation stability for
our novel metal-free dyad under ‘true energy generation’ con-
ditions, we need to improve the PCE further via metalation of
the dyad and explore an advance redox couple, electrode
materials, etc.

3.7 EIS studies

The EIS measurements of the DSSC exhibit the impedance of
the interfacial charge transport, transfer and accumulation
processes. The important charge transport occurring in the
DSSC includes electron injection in the TiO2, ionic diffusion in
the electrolyte solution, charge recombination at the electrode–
electrolyte interface, electron transfer at the counter electrode Fig. 8 (a) Nyquist plot (Z00 vs. Z 0 ) exhibiting the time constant for charge
and charging of the capacitive elements in the cell.83 The EIS transfer and recombination (a semicircle) and Warburg impedance due to
data is measured under forward bias at Voc (under no current ion diffusion (a straight line at low frequency) (an equivalent impedance
circuit is shown in the inset) and (b) Bode plot (Z vs. log F) showing
conditions) in the 0.01–100 kHz frequency range under
inflections corresponding to various impedances.
illumination. The data is displayed in the form of Nyquist
and Bode plots. A Nyquist plot shows several time constants
in terms of semicircles (usually three or less), corresponding to The middle circle is associated with the two important
specific charge transfers in the DSSC. A small semicircle in the charge transfer processes (two frequencies/time constants),
0.1 to 1 Hz range indicates the diffusion of electrolyte into the the injection of photoexcited electrons from the dye to the
solution with oD frequency (called the Nernst/Warburg diffu- TiO2 electrode (od) and the back reaction/recombination at the
sion process), a larger middle semicircle in the 1–1 kHz photoelectrode (ok). The od and ok values were obtained as
frequency range represents charge transfer at the working 95.6 and 9 Hz, from the Bode plot (Fig. 8(b)), as inflection
photoelectrode–electrolyte interface and another small semi- points that appear in the high frequency and low frequency
circle beyond the 1 kHz frequency is associated with charge regions, respectively. The od and ok frequencies are associated
transfer at the counter electrode–electrolyte interface with with two process time constants, t1 (1/od) and t2 (1/ok),
characteristic frequency, oCE.84 corresponding to electron transport/diffusion to TiO2 (injection
Fig. 8(a and b) display the EIS data measured for the DSSC at time) and electron back reaction/recombination (lifetime),
a forward bias of 0.610 V under illumination in the 0.01–100 respectively. t1–t2 also represent the charge transport in the
kHz frequency range. We identified a middle semicircle in the semiconductor/injection resistance (Rt) and the charge recom-
intermediate frequency range and an incomplete small semi- bination resistance (Rct), respectively. From the values of od
circle in the lowest frequency range converging to a line with a and ok, the two time constants were evaluated to be t1 = 1.6 ms
slope of 451 in the Nyquist plot (Fig. 8(a)). The latter accounts and t2 = 17.7 ms. It was found that t1 o t2 and Rt o Rct,
for the occurrence of a mixed type process (faradaic charge indicating that the electrons are able to reach the photoelec-
transfer and mass transfer) across the nonpolarizable electrode– trode before recombination occurs. This is an important criter-
electrolyte interface, called the Warburg impedance (W) and is ion for the functioning of the DSSC as an energy generator.
indicated as the break point in the low frequency region of the The transport properties are often summarised through the
Bode plot85 (Fig. 8(b)). The absence of a semicircle in the highest introduction of the diffusion length (Ln), which is given by:
frequency region is an indication of rapid electron exchange
between the CE and electrolyte. Ln = (t2Dn)1/2 (4)

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Table 3 Various time constants and values of important cell parameters calculated from the EIS spectra of the DSSC

Rs (O) Cdl (F) Rct (O) Rt (O) t1 (ms) t2 (ms) d (mm) Dn (mm) Ln (mm) Cm
5
43.9 6.34  10 58.0 25.2 1.648 17.69 4 0.01 13.3 2.5 1010 F

where t2 is the electron lifetime and Dn is the chemical diffusion served as a conjugated spacer between the two substituted
coefficient. Dn can be evaluated using the relationship: porphyrin moieties. The photophysical and electrochemical
measurements of this novel sensitizer reveal that it has suitable
Dn = d2/t1 (5)
energy levels for efficient electron injection and regeneration
where d is the thickness of the TiO2 film. The value of Ln was processes, when used as a sensitizer for DSSCs. The free base
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found to be 13.3 mm, even higher than the thickness of the TiO2 dyad exhibited encouraging PCE values of 6.9% with good anti-
film used (d = 4 mm), meaning that all of the photogenerated aggregation stability, and these results provide new directions
charge carriers are statistically collected. The calculated EIS and ideas for further improvements.
parameters are summarised in Table 3. The higher magnitude
of Rct, Ln and t2 than those of Rt, d and t2 suggest that the Conflicts of interest
process of electron injection into the TiO2 semiconductor is
efficient. The higher Rct observed (meaning less tendency for There are no conflicts to declare.
recombination to occur) can be correlated to the introduction
of the benzimidazole moiety, which effectively blocks the close
contact of the oxidized electrolytes with the TiO2 surface.86 The
Acknowledgements
long recombination time (t2 17.7 ms) observed is comparable The author thankfully acknowledges the funding received from
with that of a similar type of triazine linked Zn-doped porphyrin VIT Vellore through a ‘VIT SEED GRANT’ for carrying out this
dimer (16.1 ms), conveying the excellent charge separation research work. The author also acknowledges SIF DST-VITFIST,
capability of the system.67 the SEM facility at SBST and RGEMS (VIT, Vellore) and Government
The EIS data obtained is usually fitted to an equivalent Institute of Science, Nagpur for allowing the use of the analytical
impedance circuit that models a DSSC. A DSSC with two instruments. We like to extend our thanks to ‘‘Smart Materials
electrodes dipped in electrolyte is often represented as a Laboratory for Bio-Sensing and Catalysis’’ for providing basic
solid–liquid interface in terms of the Voigt element (a parallel facilities.
combination of the charge transfer resistance, Rct, and the
double layer capacitance, Cm). This is augmented by the resis-
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