TiO2 NANOPARTICLES SENSITIZED WITH MICROWAVE-AFFORDED Ru(II)

COMPLEXES TO INVESTIGATE THE PHOTOPHYSICAL RESPONSE OF

ANTENNA-COMPLEXES IN DSSC SOLAR CELLS

Jorge S. Gancheff1, Karolina Soca1, Florencia Luzardo1, Raúl Chiozzone1, Pablo A. Denis2,
Paula Enciso3, M. Fernanda Cerdá3, Reza Dousti4, Andrea S. S. de Camargo4

Cátedra de Química Inorgánica, Departamento Estrella Campos, Universidad de la República,

1

Av. Gral Flores 2124, 11800 Montevideo, URUGUAY. E-mail: jorge@fq.edu.uy

Computational Nanotechnology, DETEMA, Universidad de la República, Montevideo, URUGUAY
2

Laboratorio de Biomateriales, Facultad de Ciencias, Universidad de la República, Montevideo,

3

URUGUAY
São Carlos Physics Institute, University of São Paulo, São Carlos, SP 13566-590, Brazil
4

Abstract. The technology of converting sunlight into electricity has recently emerged as an
important strategy aimed at achieving a sustainable diversification of the energy matrix in
Uruguay and other South American countries. In this regard, photovoltaic devices appear
quite attractive because they are noiseless, present no carbon dioxide emission, and require
rather simple operation and maintenance, those of solid-state junction —usually made of
silicon— being the most important ones. This technology, which is associated with important
costs, has been challenged in the last few years by the development of a third-generation
solar cells based on conducting polymers films and nanocrystalline oxides. The so-called dye-
sensitized solar cells (DSSC) appear as a representative prototype of this family of
photovoltaic devices. They combine the optical absorption and the charge separation
processes by association of a sensitizer —as the light-absorbing material— with a wide band-
gap semiconductor of nanocrystalline morphology.

Herein, photophysical investigations of a Ru(II) novel complex (synthetized by eco-friendly

methods) of potential application as antenna in DSSC are presented. The studies cover the
response of the isolated complex in the solid state and in solution. In order to have a clear
picture of the influence of the sensitization process on the photophysical properties of
complexes, absorption/photoluminescence studies of TiO2 (anatase) nanoparticles —also
prepared by microwave-assisted reactions— sensitized with the Ru(II) complex are also
included. To get deeper insight into the electronic features of all systems, DFT calculations at
the B3LYP/LANL2DZ level of theory have also been conducted.
The technology of converting sunlight into electricity has witnessed an enormous growth in the last
few years. Solar cells have been used in different applications ranging from small consumer
electronics to megawatt-scale power plants [1]. Direct use of solar radiation to produce electricity is
perceived as an almost ideal way to employ nature´s renewable energy. Despite the significant
development over the past decades, the high cost of solar cells remains a limiting factor for the
massive implementation of solar electricity on a larger scale [2]. In contrast to conventional silicon-
based semiconductor solar cells, the dye-sensitized solar cell (DSSC) technology, which comprises a
photochemical solar cell, has emerged as an important alternative in the last few years. Since then,
many scientists have focused on the development of new and most efficient dyes. One of the most
important concerns with the synthesis of dyes for DSSCs is the use of harmful organic solvents. A
solution to this drawback has been proposed by introducing a microwave-based synthetic approach
employing eco-friendly solvents.

Herein, we present the synthesis and a spectroscopic investigation of a new Ru(II) complex of
potential application in DSSC prepared by microwave-assisted reactions in water as a benign solvent.
Then, TiO2 (anatase) nanoparticles, also synthetized by microwave irradiation, were sensitized with
the Ru(II) complex to study the photophysical behavior of dyes in DSSC conditions. Theoretical (DFT
and TD-DFT) calculations have also been performed to shed light into different electronic aspects of
the isolated and the attached dye.

The reaction path used to prepare the new Ru(II) complex involved the use of [RuCl2(p-cymene)2]2
and cis-[RuCl2(dcbipy)2] as precursor. The microwave-assisted synthetic strategy employed to obtain
[RuCl2(p-cymene)2]2 and cis-[RuCl2(dcbipy)2] allowed us to reproduce the results of Tönnenmann et
al. [3], and Kristensen et al. [4], respectively. At the same time, it prompted us to implement the
abovementioned strategy as a routine synthetic tool in our Inorganic Chemistry laboratory. Thus, we
decide to prepared a new Ru(II) complex —potential antenna in DSSC— by using MW irradiation in
water. The combination of cis-[RuCl2(dcbipy)2] and isonicotinic acid in inert atmosphere, led to the
formation of cis-[Ru(dcbipy)2(ina)2]Cl2 (Ru-ina; Scheme 1). When the reaction proceeded in an
oxidative atmosphere, we detected signals of metal oxidation (UV–VIS). The formation of the cis
isomer was ensured by the use of a temperature above 170 °C, as stated by Kristensen et al. in
preparing cis-[Ru(NCS)2(dcbipy)2] using MW tools [3].

Scheme 1. Microwave-assisted synthesis of Ru(II) complexes.

The Ru-ina complex was characterized by FT–IR and absorption/ photoluminescence spectroscopies.
The vibrational data show the asymmetric/symmetric bands for the carboxylic groups –CO2– at 1731,
1607, 1542, 1385 cm–1, and the characteristic pyridyl unit at 1385 cm–1. Two absorption bands were
detected in the visible region centered at 489 nm (asymmetric band) and at 369 nm, both of them
exhibiting almost equal intensity. Emission studies —exciting the complex with light of wavelength of
500 nm— lead to a band peaked at 550 nm. This result is in line with the behavior of the well-known
and so-called N3-sensitizer (cis-[Ru(NCS)2(dcbipy)2]), which was taken (in this work) as a model. In
this case, an emission band centered at 545 nm ( exc = 480 nm) was observed. It is worth highlighting
that N3 was prepared by microwave irradiation (Scheme 1) according to the one made available by
Kristensen et al. [4].

The microwave-assisted technique was also applied to prepare TiO2 nanoparticles (anatase)
according to the protocol of Moura et al. [5], which were sensitized with the N3-model complex and
with the new Ru(II)-complex. This process was accomplished by immersing the white nanoparticles in
an ethanolic solution of the complex during 24 h in the absence of light. Pink nanoparticles were
obtained, which indeed remained colored even after several washes with ethanol. This observation
points to a covalent anchoring of the dye to the semiconductor. This result is not surprising since
carboxylic groups are one of the most employed and effective anchoring groups of dyes in DSSC [6,7].

Luminescence investigations of the sensitized nanoparticles with the model dye (system N3@TiO2)
revealed the presence of an absorption band at 530 nm, red-shifted (+30 nm) with respect to the
free-complex. This result is in line, for instance, with the shift exhibited by N3 sensitizing Bi4Ti3O12
nanoparticles [8]. At the same time, the luminescence measurements show an emission band at 541
nm (exc = 500 nm), slightly blue-shifted (–4 nm) with respect to the free-dye. When the sensitization
process involves Ru-ina, similar findings were obtained. The UV–VIS spectrum of (Ru-ina)@TiO2 (Fig.
1) exhibits two absorption bands a 315 nm and 502 nm, the last one being measured +13 nm with
respect to the isolated dye.

DFT and TD-DFT calculations were performed for cis-[RuX2(dcbipy)2] (X– = NCS–, Cl–) and for cis-
[Ru(dcbipy)2(ina)2]2+ [9]. In particular, TD-DFT emission calculations in the presence of EtOH as
solvent have been carried out for cis-[Ru(Cl)2(dcbipy)2] [9]. This complex was used as an example to
test the reliability of the theoretical tool in reproducing emission data and in doing that, to
implement this theoretical tool in our Theoretical Chemistry Laboratory. While emission bands at 440
nm (exc of 340 nm) and at 540 nm (exc of 480 nm) have been experimentally detected for an
ethanolic solution of cis-[Ru(Cl)2(dcbipy)2], two bands at 478 nm (exc of 396 nm) and at 527 nm (exc
of 456 nm) have been calculated with B3LYP/LANL2DZ/C-PCM. These results evidenced that this
simple methodology is reliable enough to study different electronic aspects of dyes —potential
antenna in DSSC—, with a reasonable computational cost.

For Ru-ina, TD-DFT absorption data (Fig. 1) are available; no emission theoretical results were
obtained so far. The simulated UV–VIS spectrum [9] in ethanol was in reasonable agreement with the
experimental evidence. The excitations responsible for the band in the visible region involve starting
MOs of mainly metallic character, while destination MOs are located on ligands (dcbipy and ina) (Fig.
1). These results helped us to infer the origin of the band experimentally observed at 502 nm for (Ru-
ina)@TiO2 as metal-to-ligand charge transfer (MLCT). The band in the high-energy part of the
spectrum (315 nm) seems to present the same origin (MLCT), with the electronic density moving
from a metal-centered MO to a MO mainly located on the bipyridyl unit of the dcbipy anchoring
ligands. It is worth mentioning that the sensitization process promoted an increase of the intensity of
this band with respect to this band in the free-complex. As aforementioned, the contour of
destination MO in the MLCT band at 315 nm displays charge delocalization on the bipyridyl unit of
the dcbipy ligands. This finding suggests that the carboxyl groups, which act as a linkage group, are
the ones located on the dcbipy ligands and not those of the ina ligand. To confirm this assumption,
theoretical investigations of different electronic aspects of the Ru-ina@TiO2 system at the DFT level
of theory are undertaken.

In conclusion, the microwave-assisted tool has been successfully employed in yielding model Ru(II)
antenna-complexes in DSSC. At the same time, it has proven to be adequate and eco-friendly to
prepare new Ru(II) compounds. In this line, the complex cis-[Ru(dcbipy)2(ina)2]Cl2 has been obtained
and characterized. It has been used to sensitize the surface of TiO2 (anatase) nanoparticles, which
have also been afforded by microwave techniques. Luminescence studies of the new Ru(II) complex
lead to results in line with the ones obtained for model complexes, which point out that the new
complex present potential application as antenna in DSSC. The sensitization of the semiconductor
surface does not significantly change the photophysical features of the attached dye. With assistance
of theoretical (DFT) calculations, the sensitization of nanoparticles could be a reasonable model to
study different electronic aspects of dyes in DSSC operative conditions.

Figure 1. TD-DFT result of (Ru-ina) (dashed line), and experimental UV–VIS spectrum of Ru-ina@TiO 2 (solid
line). Most important MOs involved in the origin of the simulated bands for Ru-ina are also included.

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Acknowledgements

This work was supported by Agencia Nacional de Investigación e Innovación (ANII, Proy. FSE_1_2011_1_6156).
We are also indebted to PEDECIBA-Química. A.S.S.C. would like to thank FAPESP (Fundação de Amparo à
Pesquisa do Estado de São Paulo, Brazil) for the financial support (Cepid Project 2013/07793-6).