Coordination Chemistry Reviews 248 (2004) 1343–1361

Review
Metal complex sensitizers in dye-sensitized solar cells
André Sarto Polo, Melina Kayoko Itokazu, Neyde Yukie Murakami Iha∗
Laboratory of Inorganic Photochemistry and Energy Conversion, Instituto de Quı́mica,
Universidade de São Paulo, Av. Prof. Lineu Prestes, 748-05508-900 São Paulo, SP, Brazil

Received 28 December 2003; accepted 20 April 2004

Dedicated to Professor Michael Grätzel in recognition of his achievements.
Available online 25 June 2004

Contents
Abstract . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1343
Ligands . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1344
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1347
2. Overview . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1348
3. Dye-sensitized solar cells . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1349
4. Photosensitizers. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1349
4.1. Metal complex sensitizers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1349
4.1.1. Series of cis-[Ru(dcbH2 )2 LL ] . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1350
4.1.2. Non-carboxylic acid anchoring group ruthenium complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1353
4.1.3. Other d6 complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1353
4.2. Natural sensitizers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1354
5. Closing remarks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1357
5.1. Work on Dye-cell at the IQ/USP, Brazil. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1358
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1358
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1358

Abstract

A brief review of the investigation of solar energy conversion and the development of dye-sensitized thin-layer solar cells is presented, with
the main focus on dyes, specially on d6 metal complexes employed, since 1998, as photosensitizers of nanocrystalline semiconductors. An
extensive literature coverage of the spectroscopic properties and the performance of solar cells employing a series of cis-[Ru(dcbH2 )2 LL ]
species, in which dcbH2 is 4,4 -(CO2 H)2 -2,2 -bipyridine and L and/or L are ancillary ligands, is presented along with non-carboxylic acid
anchoring polypyridine-ruthenium complexes. The utilization of other d6 metal complexes and natural extracts, with emphasis on Brazilian
products, is also reviewed. A list of ligands with structures and a series of Tables summarize the collected data. The research and development
on dye-sensitized solar cells conducted at our Laboratory of Inorganic Photochemistry and Energy Conversion at the University of São
Paulo-Brazil is also covered in this context as a part of this special issue in homage to Prof. Grätzel.
© 2004 Elsevier B.V. All rights reserved.

Keywords: Dye-cells; Sensitizers; Dye-sensitized solar cells; Natural dyes; Energy conversion; Photoelectrochemical solar cells

Abbreviations: AN, acetonitrile; APCE, absorbed photon-to-current efficiency; Black Dye, [Ru(tcterpy)(NCS)3 ]− ; DMF, dimethylformamide; DMSO,
dimethyl sulfoxide; Dye-cell, dye-sensitized solar cell; EG, ethylene glycol; EtOH, ethanol; ff, fill factor; FTO, fluorine doped tin oxide; HOAc, acetic acid;
IPCE, incident photon to current efficiency; Isc , short circuit current; ITO, indium doped tin oxide; MeOH, methanol; MLCT, metal to ligand charge transfer;
3-MPN, 3-metoxypropionitrile; N3, cis-[Ru(dcbH2 )2 (NCS)2 ]; NMO, 3-methyl-2-oxazolidinone; PC, propylene carbonate; TBA, tetrabutylamonium; TCO,
transparent conducting oxide; TFMS, trifluoromethylsulfonate; THF, tetrahydrofuran; Voc , open circuit voltage; ε, molar absorptivity; η, quenching
efficiency; ηcell , overall efficiency; λ, wavelength
∗ Corresponding author. Tel.: +55 11 3091 2151; fax: +55 11 3815 5579.

E-mail address: [email protected] (N.Y. Murakami Iha).

0010-8545/$ – see front matter © 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.ccr.2004.04.013
1344 A.S. Polo et al. / Coordination Chemistry Reviews 248 (2004) 1343–1361

Ligands

Name Abbreviation Structure

Pyridine py

4-Thiopyridine pySH

Isoquinoline isq

4-Phenylpyridine ppy

4-Cyanopyridine CNpy

Isonicotinic acid isn

2,2 -Bipyridine bpy

3,3 -Dicarboxylic acid-2,2 -bipyridine 3,3 -dcbH2

4,4 -Dicarboxylic acid-2,2 -bipyridine dcbH2

5,5 -Dicarboxylic acid-2,2 -bipyridine 5,5 -dcbH2

4,4 -Dinitro-2,2 -bipyridine bpy-(NO2 )2

4,4 -Dihydroxymethyl-2,2 -bipyridine bpy-(CH2 OH)2

4,4 -dicarboxylate-diethyl 2,2 -bipyridine bpy-(CO2 Et)2

4-(Lithium carboxymethyl)-4 -methyl-2,2 -bipyridine bpy-CH2 COOLi

4-(1,1-Dilithiumcarboxymethyl)-4 -methyl-2,2 -bipyridine bpy-CH(COOLi)2

4,4 -(1,1-Dilithiumcarboxymethyl)-2,2 -bipyridine bpy-(CH(COOLi)2 )2

4-[4-Oxo-5-(ethoxycarbonyl)pentyl]-4 -methyl-2,2 bipyridine bpy-acac

A.S. Polo et al. / Coordination Chemistry Reviews 248 (2004) 1343–1361 1345

Name Abbreviation Structure

4,4 -Dimethyl-2,2 -bipyridine dmbpy

4,4 -Dihydroxamic acid-2,2 -bipyridine dobH2

3-Dihydroxy phosphinyl-cis-4-(4 -methyl-2,2 -bipyridine- pbp-pra

4-carboxamido)-l-proline-N-carboxylic acid

3,5-Bis(dihydroxy bpb-pra
phosphinyl)-N-(1,1-dimethoxycarbonyl)-cis-4-(4 -
methyl-2,2 -bipyridine-4-carboxamido)-l-proline methyl
ester

4-Phosphonic acid-2,2 -bipyridine bpy-PO3 H2

4,4 -Biphosphonic acid-2,2 -bipyridine bpy-(PO3 H2 )2

5,5 -Biphosphonic acid-2,2 -bipyridine 5,5 -bpy-(PO3 H2 )2

4,4 -Dietyl ester phosphonate-2,2 -bipyridine bpy-(PO3 Et2 )2

2,2 -Bipyridine-4,4 -disulphonic acid-2,2 -bipyridine dsbpy

1,10-Phenanthroline phen

Phendione phendione

Phendioxime phendioxime

2,2 -Biquinoline biquin

4-([1,10]Phenanthrolin-5-yliminomethyl)-phenol aphb
1346 A.S. Polo et al. / Coordination Chemistry Reviews 248 (2004) 1343–1361

Name Abbreviation Structure

2,3-Dihydroxydipyrido[3,2-f:2 ,3 -h] quinoxaline dpq(OH)2

2,4-(1,3-N,N -Dimethyl)pteridinedione dmp

6,7-Dimethyl-2,4-(1,3-N,N -dimethyl) pteridinedione mdmp

6,7-Diphenyl-2,4-(1,3-N,N -dimethyl) pteridinedione phdmp

6,7-Bis(pyrid-2-yl)-2,4-(1,3-N,N -dimethyl) pteridinedione pydmp

Dibenzo[h,j]-(1,3-N,N -dimethyl)isoalloxazine bIAlo

2,6-Bis(1-methylbenzimidazol-2-yl)pyridine bmipy

4,4 ,4 -Tricarboxylic acid-2,2 :6 ,2 -terpyridine tc-terpy

4-Phosphonic acid-2,2 :6,2 -terpyridine hp-terpy

4 -(4-Phosphonic acid phenyl)-2,2 :6 ,2 -terpyridine ttp-PO3 H2

4 -(3,4-Dihydroxyphenyl)-2,2 :6 ,2 -terpyridine dhpt

A.S. Polo et al. / Coordination Chemistry Reviews 248 (2004) 1343–1361 1347

Name Abbreviation Structure

4 ,4 -Diethoxycarbonyl-2,2 :6 ,2 :6 ,2 -quaterpyridine detOq

3-(2-Hydroxyphenyl)-5-(pyridin-2-yl)-1,2,4-triazole 2-ppt

3-(4-Hydroxyphenyl)-5-(pyridin-2-yl)-1,2,4-triazole 4-ppt

3,5-Bis(pyrazin-2-yl)-1,2,4-triazole bpzt

3-(2-Hydroxyphenyl)-5-(pyrazin-2-yl)-1,2,4-triazole 2-ppzt

Quinoxaline-2,3-dithiolate qdt

Ethyl-2-cyano-3,3-dimercaptoacrylate ecda

1,2-Benzenedithiolate bdt

3,4-Toluenedithiolate tdt

N,N -Diethyldithiocarbamate ddtc

Acetylacetonate acac

3-Methyl-2,4-pentanedionate mpdionate

1,3-Diphenyl-1,3-propanedionate dphdionate

1. Introduction devices, and it is one of the new approaches for photovoltaic

technology. This device is based on chemical concepts, in
An energy system infrastructure is fundamental for world- which the separation of charge carriers is kinetically con-
wide technological and economic achievements. In the 21st trolled by the chemical reactions involved. The tasks of light
century, fossil fuel based energy has to be replaced by new absorption and charge carrier transport are separated in a
energy systems by incorporating novel technologies derived Dye-cell by having the light absorbed by sensitizers (dyes)
from advancements in science [1]. Renewables are the per- chemically attached to the surface of a nanostructured wide
spective for future energy needs and the key to sustainable band-gap semiconductor (mesoporous oxides); they there-
development. fore do not require an intrinsic electric field.
Solar photovoltaic cells, capable of directly converting The simple materials employed in production provide an
sunlight into electrical power, are one of the most promising efficient and low cost solar cell. Moreover, the process gen-
devices in the search for sustainable and renewable sources erates a very little residue. Thus among several other advan-
of clean energy [2,3]. Although the field had been dominated tages, the low environmental impact [7,8] and reduced en-
in the last years of the past century by technology based on ergy demand in the production of dye-sensitized solar cells
the solid-state p–n junction devices, a new generation of pho- [1] are certainly worth emphasizing [1,8,9].
tovoltaics is now emerging. One of them is the dye-sensitized In this special issue in homage to Prof. Grätzel, a brief
nanocrystalline solar cell [4–6], named by us as Dye-cell. review of thin-layer solar cells based on the sensitization
The Dye-cell is the result of exploiting several new con- of the wide band-gap TiO2 semiconductor films by some
cepts and materials, such as nanotechnology and molecular metal complexes or natural dyes will be presented. The
1348 A.S. Polo et al. / Coordination Chemistry Reviews 248 (2004) 1343–1361

main focus will be on dyes, specially on d6 metal complexes turability as well as historical overview have been the sub-
employed during the last few years as photosensitizers of ject of recent reviews [1,9,48] and will not be covered here.
nanocrystalline semiconductors. Due to the page limit of Several books and other review papers [4,6,46,49–52] have
this issue, an extensive literature coverage of spectroscopic already discussed different aspects of dye-sensitized solar
properties and performance in solar cells has been limited cells, but two of them are particularly worthwhile for visual-
for a series of ruthenium(II) complexes of bis(dicarboxylic izing research horizons in this field [6,46]. Kalyanasundaram
acid bipyridine), cis-[Ru(dcbH2 )2 LL ], in which dcbH2 is and Grätzel presented an instructional and wide coverage
4,4 -(CO2 H)2 -2,2 -bipyridine and L and/or L are ancillary in their 1998 review [46]; this being one of the reasons for
ligands, and for ruthenium complexes with polypyridine this work to focus on papers published from 1997/1998 up
ligands having non-carboxylic acid anchoring groups. The to now. Updated results and ongoing investigation can now
utilization of natural sensitizers, including several Brazilian be followed in this and other papers of this special issue;
natural products, as well as other d6 sensitizers is also re- therefore, only the basic principles required for understand-
viewed. A list of ligands and a series of tables summarize ing the subjects discussed here will be briefly presented in
the data collected. this review.
The research and development on dye-sensitized solar Historically, chemically-based systems such as photogal-
cells conducted at our Laboratory of Inorganic Photo- vanic and photoelectrochemical cells have been developed
chemistry and Energy Conversion at the University of São [51,52] as an alternative to the conventional solid-state p–n
Paulo-Brazil is also covered in this context as a part of this junction photovoltaics for the conversion of solar energy into
special issue to provide a perspective for some of our rep- electricity.
resentative experimental results and to place our own work The use of coordination compounds, such as [Ru(bpy)3 ]2+ ,
in this field. as light absorbers, was one of the first approaches to convert
The studies carried out in our Laboratory had been ini- low-energy starting materials into high-energy products in
tially focused on kinetics, electrochemistry and spectroscopy homogeneous cells, although with low efficiencies due to
of some inorganic compounds with emphasis on the reac- the fast recombination of the photoproducts in the solution
tivity of the ground state [10–22], followed by investigation [51].
on the photoreactivity of these compounds [11,23–27]. Our Photoelectrochemical cells seemed to be the answer to ac-
interests have also been extended to supramolecular pho- complish this conversion, but early experiments resulted in
tochemistry [28–30], photosensors [31–35] and nanocrys- low photocurrent generation [51,53]. The use of photostable
talline semiconductor sensitization [1,5,28,29,36–44]. This wide band-gap semiconductors required high-energy light to
natural step had positive inputs through important collabo- create electron–hole pairs and the effectiveness of dye sen-
rations established with Prof. Carlo A. Bignozzi and Prof. sitization was restricted by the surface area of TiO2 crystals,
Thomas J. Meyer. A very important additional motivation re- sub-monolayer coverage and low absorptivities [54]. It did
sulted from very fruitful discussions maintained since 1997 however present advantages over direct band to band excita-
with the Lausanne Group through Prof. Grätzel and Dr. tion of semiconductors due to the reduction of electron–hole
Nazeeruddin. recombination.
During our visit in their Laboratory at EPFL in 1998, the Semiconductors in mesoporous membrane type film with
ensuing discussion strongly encouraged us in our incipient a high surface area led to an efficient light absorption by
investigation of natural dyes. Both their enthusiasm and sim- attached sensitizers and resulted in intensely colored pho-
ilar objectives have provided a driving force for our research toanodes. Solar cells employing such photoanodes presented
in such an interdisciplinary area. astonishing results, with photoresponse 1000 times higher
for the nanostructured electrode [49,55]. In the early 1990s
the development of extremely rough TiO2 and an efficient
photosensitizer led to photoelectrochemical solar cells rec-
2. Overview ognized as an efficient device for conversion of solar energy
into electricity [6].
The dye-sensitized solar cell is a particularly interesting In this approach, attached dyes, rather than the semicon-
case of an integrated chemical system [45,46], in which a ductor itself, are the absorbing species. They inject electrons
device is designed and molecularly engineered to perform into the semiconductor conduction band upon excitation.
light conversion into electricity. It is a fascinating multidis- These electrons are then collected at a conducting surface,
ciplinary topic of current interest and a very active research generating photocurrent. As a result of this advance, the de-
field, which has attracted wide attention in the last decade. It velopment of low-cost, efficient photochemical solar cells
also illustrates an application that has evolved from funda- became possible [6,56].
mental investigation to the concept of specifically designed The field experienced steady progress since then and
artificial molecular devices [47]. dye-sensitized photoelectrochemical solar cells attained the
The device itself, operating principles, stability, theoret- required maturity to become a noteworthy device for pro-
ical background, state of the art, technology and manufac- duction [9,57,58]. Due to the multitude of issues related to
A.S. Polo et al. / Coordination Chemistry Reviews 248 (2004) 1343–1361 1349

dye-sensitized solar cells, investigations are currently spread sintering around 450 ◦ C are usually used to provide textured
over a wide range of fields. The research is supported by semiconductor substrates with nanocrystalline structure.
contributions from interdisciplinary domains in several as- The sensitization of wide band gap nanocrystalline semi-
pects, such as molecular engineering and syntheses of new conductor oxides by dyes has been intensively investigated
dyes, TCO and semiconductor materials, electrolyte media, and a strategy to obtain both the photosensitizer and the in-
long-term stability of the devices, theoretical studies of the terface through molecular engineering is one of the most at-
photoconversion process and so on. tractive approaches to improve the performance of the cell.
Thus, the following items of this review are dedicated to
photosensitizers, with the main focus on metal complex sen-
3. Dye-sensitized solar cells sitizers.
The photoexcitation of sensitizer and subsequent electron
Regenerative photoelectrochemical solar cells based on a injection into the conduction band of the semiconductor
thin-layer sandwich-type set-up containing a dye-sensitized allows population of the band using light of energy lower
nanocrystalline TiO2 photoanode are now commercially fea- than the semiconductor band gap, and can provide a good
sible devices. match with the solar spectrum. The oxidized sensitizer (S+ )
Dye sensitization has provided a successful solution to is quickly reduced back to S by the redox mediator couple,
extending the absorption range of the cells to low-energy usually I3 − /I− , present in the electrolyte and this is, in turn,
light with effective results. This approach presents advan- regenerated at the counter electrode, concluding the redox
tages over the direct band-to-band excitation in conventional cycle. The reduction of I3 − is catalyzed by small amounts
solar cells, since attached dyes, rather than the semicon- of Pt deposited on the counter electrode. Therefore, in this
ductor itself, are the absorbing species and the processes of regenerative electrochemical device, visible light is effi-
light absorption and charge separation are separated by the ciently converted into electricity without any permanent
semiconductor/sensitizer interface preventing electron–hole chemical change.
recombination [28,29,59–67]. Electron injection from the The performance of the cell can be quantified on a macro-
photoexcited sensitizer into the semiconductor conduction scopic level with parameters such as Incident Photon to Cur-
band occurs with energy lower than the band gap, providing rent Efficiency, IPCE, open circuit photovoltage, Voc , and
good sunlight harvesting by sensitizers (dyes) which exhibit the overall efficiency of the photovoltaic cell, ηcell . Several
broad absorption bands in the visible region. parameters such as the spectroscopic and redox properties
A typical dye-sensitized solar cell is depicted in Fig. 1. of dyes, the efficiency of charge injection and the structural
The device is constituted of two transparent conducting ox- properties/characteristics of the semiconductor electrode to
ide substrates, TCO, such as fluorine doped tin oxide, FTO, collect and direct electrons through the external circuit are
on glass or polymeric substrates [4,68]. One TCO is a pho- relevant to determine the photocurrent values and will cer-
toanode, composed of a sensitizer adsorbed onto the sur- tainly be subjects of several reviews in this special issue.
face of the nanocrystalline semiconductor electrode (typi-
cally nanostructured TiO2 ), and the other a photoinert coun-
terelectrode with a thin layer of a catalyst (for instance, plat- 4. Photosensitizers
inum) sandwiching an electrolyte/relay medium (usually a
solution containing the I3 − /I− pair). An efficient photosensitizer should fulfill some require-
n-TiO2 is the most employed semiconductor material in ments such as an intense absorption in the visible region,
dye-sensitized photoelectrochemical solar cells due to its fa- strong adsorption onto the semiconductor surface and effi-
vorable energetics, stability, low price and facile processing cient electron injection into the conduction band of the semi-
[68–71]. Semiconductor colloids are typically obtained via a conductor. Moreover, it must be rapidly regenerated by the
sol–gel process from titanium isopropoxide or directly from mediator layer in order to avoid electron recombination pro-
commercial TiO2 . Whereas the preparation of colloids from cesses and be fairly stable, both in the ground and excited
Degussa TiO2 is easier and faster, the isopropoxide hydrol- states. Many different compounds have been investigated for
ysis method results in transparent to translucent semicon- semiconductor sensitization, such as porphyrins [72,73,55],
ductor films [5]. Screen printing of TiO2 sol followed by phthalocyanines [74–81], coumarin 343 [82,83], carboxy-
lated derivatives of anthracene [84,85] and polymeric films.
Among the photosensitizers investigated, transition metal
complexes have been the best so far [1,46].

4.1. Metal complex sensitizers

Metal complexes sensitizers usually have anchoring lig-

ands and ancillary ligands. Anchoring ligands are respon-
Fig. 1. Thin-layer sandwich-type solar cell and its components. sible for the complex adsorption onto the semiconductor
1350 A.S. Polo et al. / Coordination Chemistry Reviews 248 (2004) 1343–1361

surface and are also chromophoric groups. Ancillary lig- onto semiconductor surface, while its properties can be tuned
ands are not directly attached onto the semiconductor sur- by using different ancillary ligands. Most efficient energy
face and can be used for tuning the overall properties of the conversion has been observed using bis-(4,4 -dicarboxylic
complexes. acid-2,2 -bipyridine), (dcbH2 )2 , as anchoring ligands lead-
Polypyridinic complexes of d6 metal ions show intense ing to these complexes becoming one of the most important
metal to ligand charge transfer (MLCT) bands in the visible classes of photosensitizer investigated so far.
region with potential interest for promoting charge injection An outstanding result was reported in 1993 by Grätzel
processes to the conduction band of wide band gap semi- and co-workers with the cis-[Ru(dcbH2 )2 (NCS)2 ] photo-
conductors, such as TiO2 , SnO2 and ZnO. The energies of sensitizer, also known as N3 [97]. Since then it has been
the MLCT states can be altered systematically by modifying employed as a standard dye in several studies, especially
the anchoring ligands as well as by changing the ancillary to compare the performance of other dyes [43,88,98–101]
ligands or its substituents. or the results of modifications introduced in semiconductor
The wide possibilities to tune the MLCT energy led to composition/treatment [102], as noted in Table 1.
the preparation of many different compounds that have been Ever since N3 was reported as a very efficient energy con-
investigated for semiconductor sensitization. Among them, version dye, efforts have been made to either match or im-
the best light-to-electricity conversion efficiency has been prove its performance. One approach that has been attempted
achieved by using ruthenium(II) polypyridyl complexes as by several investigators is the substitution of the NCS− ancil-
TiO2 sensitizers in dye-sensitized solar cells. Ruthenium lary ligands. This search for efficient cis-[Ru(dcbH2 )2 LL ]
polypyridinic complexes have been intensively employed as sensitizers has led to a wide variety of new photosensitizers.
sensitizers due to their appropriate redox, spectroscopic, and Their spectroscopic properties are listed in Table 2, while
excited-state properties [86–93]. In particular ruthenium(II) their performance in solar cells is shown in Table 3. Even
complexes with carboxylic pyridine derivatives are able to though the main focus is the performance, the data in Table 2
react readily with oxide surfaces to form the corresponding are also relevant as far as an understanding of these results
esters [46], presenting efficient adsorption onto the semi- is concerned.
conductor surface and improved light harvesting efficiency, Data presented in Table 3 point out that the substitution
leading to fine results. Due to the page limit we will re- of the ancillary ligands has not, so far, improved the per-
strict our review to a series of ruthenium(II) complexes of formance of the cells in terms of overall efficiency, ηcell , or
bis(dicarboxylic acid bipyridine), dcbH2 , although remark- IPCE values, even though the new dyes could be success-
able performance has been observed for other ruthenium sen- fully employed as semiconductor sensitizers. On the other
sitizers such as [Ru(tcterpy)(NCS)3 ]− , the so called Black hand, these new photosensitizers usually provide a wider
Dye [94–96]. coverage of the solar spectrum, promoting light harvesting
in a lower energy region. The MLCT bands are suscepti-
4.1.1. Series of cis-[Ru(dcbH2 )2 LL ] ble to a greater electron donating or withdrawing ability of
Several studies have been carried out using [Ru(dcbH2 )2 the ancillary ligand as can be seen in a series of complexes
LL ] as dyes. The main idea behind these complexes is to using pteridinediones or diimine thiolates [91,105]. Such
have a good anchoring ligand to allow an efficient adsorption transitions are sensitive to changes made in the anchoring

Table 1
Photoelectrochemical data obtained with solar cell sensitized by cis-[Ru(dcbH2 )2 (NCS)2 ]
Voc (V) Isc (mA cm−2 ) IPCEmax (%) ff ηcell (%) Remarks Reference

82.4 [102]
0.698 17.9 >80 0.56 7.4 [101]
0.662 14.5 0.55 6.8 [100]
0.640 16.5 0.65 [99]
0.55 10.4 0.52 2.99 [98]
0.70 15.0 80 0.74 7.8 [87]
0.57 18.4 67 [103]
17.5–18.5 80 [104]
0.61 6.4 0.42 6.1 [88]
0.640 5.0 0.76 10.4 a ,b [97]
0.660 7.9 0.76 10.4 a ,c [97]
0.670 11.5 0.74 10.3 a ,d [97]
0.720 18.2 0.73 10.0 a ,e [97]
a AM 1.5, light intensity.
b 24.1 mW cm−2 .
c 38.2 mW cm−2 .
d 55.6 mW cm−2 .
e 96.0 mW cm−2 .
A.S. Polo et al. / Coordination Chemistry Reviews 248 (2004) 1343–1361 1351

Table 2
Spectroscopic parameters of cis-[Ru(dcbH2 )2 LL ] evaluated as photosensitizers
Complex Solvent λmax (nm) (εmax (104 M−1 cm−1 )) Reference

[Ru(dcbH2 )2 (dmp)]Cl2 EtOH 314 (1.68), 362 (sh), 514 (0.22) [105]
[Ru(dcbH2 )2 (mdmp)]Cl2 EtOH 246 (3.0), 316 (2.57), 364 (1.7), 550 (0.75) [105]
[Ru(dcbH2 )2 (phdmp)]Cl2 EtOH 314 (2.67), 366 (0.84), 410 (sh), 552 (0.33) [105]
[Ru(dcbH2 )2 (blAlo)]Cl2 EtOH 314 (1.55), 388 (0.615), 532 (0.52) [105]
[Ru(dcbH2 )2 (pydmp)]Cl2 EtOH 300 (0.34), 355 (0.22), 440 (0.75), 512 (0.56) [105]
[Ru(dcbH2 )2 (aphb)] DMF 350, 466 [98]
poly[Ru(dcbH2 )2 (aphb) DMF 350, 476 [98]
[Ru(dcbH2 )2 (CNpy)(H2 O)]2+ AN 310, 490 [39]
[Ru(dcbH2 )2 (CNpy)(H2 O)]2+ /TiO2 500
Ru(dcbH2 )2 (qdt) EtOH/MeOH 310 (2.58), 403 (0.94), 476 (0.86), 517 (0.88) [91]
Ru(dcbH2 )2 (ecda) EtOH/MeOH 313 (3.21), 402 (1.75), 500 (0.84), 582 (0.98) [91]
Ru(dcbH2 )2 (bdt) EtOH/MeOH 309 (3.23), 463 (0.95), 662 (0.21) [91]
Ru(dcbH2 )2 (tdt) EtOH/MeOH 307 (3.20), 470 (0.96), 670 (0.20) [91]
[Ru(dcbH2 )2 (isq)2 ]2+ /TiO2 MeOH 220, 305, 362, 471 [37,38]
[Ru(dcbH2 )2 (ppy)(H2 O)]2+ ∼525
[Ru(dcbH2 )2 (ppy)(H2 O)]2+ /TiO2 MeOH 252, 313, 378, 519 [36,38]
[Ru(dcbH2 )2 (ppy)2 ]2+ ∼500
[Ru(dcbH2 )2 (ppy)2 ]2+ /TiO2 MeOH 253, 307, 366, 485 [36,38]
[Ru(3,3 -dcbH2 )2 (NCS)2 ] DMF 572 [103]
[Ru(5,5 -dcbH2 )2 (NCS)2 ] DMF 585 [103]
[Ru(dcbH2 )2 Cl2 ] EtOH 304, 380, 540 [88]
[Ru(dcbH2 )2 (acac)]Cl NaOH/MeOH 309 (5.35), 384 (1.46), 525 (1.35) [106]
[Ru(dcbH2 )2 (mpdionate)]Cl NaOH/MeOH 310 (5.10), 386 (1.41), 532 (1.21) [106]
[Ru(dcbH2 )2 (dphdionate)]Cl NaOH/MeOH 309 (5.76), 378 (1.37), 514 (1.37) [106]
Ru(dcbH2 )3 Cl2 H2 O 303, 352, 458 [88]
[Ru(dcbH2 )2 (4-ppt)] AN 495 [107]
[Ru(dcbH2 )2 (2-ppt)] AN 495 [107]
[Ru(dcbH2 )2 (bpzt)] AN 475 [107]
[Ru(dcbH2 )2 (2-ppzt)] AN 475 [107]
[Ru(dcbH2 )2 (ddtc)] EtOH 312 (3.35) 364 (0.97), 548 (1.13) [108]
Ru(dcbH2 )2 (NCS)2 EtOH 314 (4.94) 398 (1.31), 538 (1.31) [108]
Bibliography since 1998.

group, dcbH2 , and the distinct positioning of the carboxylic

group can also promote absorption shifts [103] and be con-
veniently employed to tune the spectroscopic response of
the sensitizer.
The proper selection of the ancillary ligands L and L in
these complexes, provides the suitable energetic control of
the properties of the species. Different compounds with ap-
propriate characteristics can be molecularly engineered en-
abling the design of efficient sensitizers of TiO2 for photo-
electrochemical solar cells. The two ancillary ligands, co-
ordinated to the non-attached side of the dye, can be con-
veniently replaced in order to adjust or tune the absorption
bands to low-energy wavelengths, thus enhancing its spec-
troscopic response to the visible light [37,38,109–112].
The contribution of our group in the design of photo-
sensitizers has been based on our experience in molec-
ularly engineering metal complexes and a knowledge of
their photophysics and photochemical properties [28,29].
For instance, based on the properties previously de-
scribed for Re(I) carbonyl complexes with isoquinoline,
isq, and 4-phenylpyridine, ppy [113,114], we have pre-
pared a series of cis-[Ru(dcbH2 )2 LL ] complexes (Fig. 2)
in which L and/or L are substituted pyridines, such as Fig. 2. Schematic representation of interfacial electron transfer following
cis-[Ru(dcbH2 )2 (isq)2 ]2+ and cis-[Ru(dcbH2 )2 (ppy)2 ]2+ , light absorption for cis-[Ru(dcbH2 )2 LL ] with some ancillary ligands.
1352 A.S. Polo et al. / Coordination Chemistry Reviews 248 (2004) 1343–1361

Table 3
Photoelectrochemical data obtained with solar cell sensitized by cis-[Ru(dcbH2 )2 LL ]
Complex Voc (V) Isc (mA cm−2 ) IPCEmax (%) ff ηcell (%) Reference

[Ru(dcbH2 )2 (dmp)]Cl2 0.289 0.315 33.24 0.55 2.0 [105]

[Ru(dcbH2 )2 (mdmp)]Cl2 0.330 0.400 42.21 0.61 3.2 [105]
[Ru(dcbH2 )2 (phdmp)]Cl2 0.420 0.604 63.74 0.38 3.8 [105]
[Ru(dcbH2 )2 (blAlo)]Cl2 0.320 0.390 41.15 0.45 2.2 [105]
[Ru(dcbH2 )2 (pydmp)]Cl2 0.212 0.220 48.36 0.65 2.5 [105]
[Ru(dcbH2 )2 (aphb)] 0.58 5.5 0.48 1.51 [98]
poly[Ru(dcbH2 )2 (aphb)] 0.34 2.1 0.48 0.33 [98]
[Ru(dcbH2 )2 (CNpy)(H2 O)]2+ ∼60 [38,39]
Ru(dcbH2 )2 (qdt) 0.595 11.1 45 0.70 3.7 [91]
Ru(dcbH2 )2 (ecda) 0.580 5.4 30 0.65 2.0 [91]
Ru(dcbH2 )2 (bdt) 0.540 2.1 7 0.66 0.7 [91]
Ru(dcbH2 )2 (tdt) 0.504 1.1 0.70 0.4 [91]
[Ru(dcbH2 )2 (isq)2 ]2+ ∼40 [37,38]
[Ru(dcbH2 )2 (ppy)(H2 O)]2+ >50 [38]
[Ru(dcbH2 )2 (ppy)2 ]2+ ∼40 [38]
[Ru(3,3 -dcbH2 )2 (NCS)2 ] 0.47 8.0 21 [103]
[Ru(5,5 -dcbH2 )2 (NCS)2 ] 0.49 7.8 37 [103]
[Ru(dcbH)2 Cl2 ] 0.57 2.6 0.38 2.1 [88]
[Ru(dcbH2 )2 (acac)]Cl 0.674 13.20 >50 0.68 6.0 [106]
[Ru(dcbH2 )2 (mpdionate)]Cl 0.677 8.56 0.67 3.9 [106]
[Ru(dcbH2 )2 (dphdionate)]Cl 0.689 8.67 0.68 4.0 [106]
Ru(dcbH2 )3 Cl2 0.52 1.0 0.37 0.7 [88]
[Ru(dcbH2 )2 (ppt)] ∼60 [107]
[Ru(dcbH2 )2 (2-ppt)] ∼60 [107]
[Ru(dcbH2 )2 (bpzt)] ∼65 [107]
[Ru(dcbH2 )2 (2-ppzt)] ∼55 [107]
Bibliography since 1998.

as n-TiO2 sensitizers, which resulted in efficient pho- tween the charge transfer excited state of the sensitizer and
toelectrochemical solar cells [37]. The use of ancil- the wavefunction of the semiconductor conduction band.
lary ligands enables the possibility to tune the spectro- As a consequence, excitation of these complexes with visi-
scopic response of the dyes [37], and our first sensitizer ble light results in a very fast electron transfer through the
cis-[Ru(dcbH2 )2 (isq)2 ]2+ showed good light harvesting carboxylic groups to the semiconductor as described in the
and efficient electron injection, successfully converting literature [115–118]. Fig. 2 illustrates the electron injection
visible light to electrical output with IPCE values as into the semiconductor from these photosensitizers with
high as 50% up to 550 nm [37]. A higher efficiency some ancillary ligands employed in our studies.
has been observed for cis-[Ru(dcbH2 )2 (ppy)(H2 O)]2+ The excited state properties of cis-[Ru(dcbH2 )2 (ppy)2 ]2+
and cis-[Ru(dcbH2 )2 (CNpy)(H2 O)]2+ , where CNpy is were also investigated by laser flash photolysis [119], show-
4-cyanopyridine [38]. The results obtained with these ing that the kinetics of charge recombination is much slower
molecular sensitizers showed performance much better than than the ultrafast electron injection. The difference of several
those obtained with the same ancillary ligands, i.e. L = L . orders of magnitude between these processes is essential to
Interestingly, the heteroleptic complex, with different an- the successful operation of the photoelectrochemical cell.
cillary ligands, led to considerably higher IPCE values and Further examination of charge recombination and quench-
a broader spectroscopic response at longer wavelengths in ing processes, following the electron transfer across the
comparison to the homoleptic one, as can be observed in excited dye/semiconductor interface, has been investigated
Fig. 3. One approach for a molecular design of efficient with cis-[Ru(dcbH2 )2 (CNpy)(H2 O)]Cl2 attached to TiO2
photosensitizers is the control of the number of azine ancil- films. These time-resolved experiments emphasized the im-
lary ligands, which play an important role in spectroscopic portance of the efficient capture of the oxidized dye by the
sensitivity, tuning the overall properties of the complexes electron relay in solution to direct the electron transport
[37,38]. process to the desired pathway preventing the recombina-
All these compounds have broad absorption spectra with tion of the injected electron with the oxidized sensitizer.
intense MLCT bands overlapping the solar spectrum, along The analysis of experiments on TiO2 photoanodes func-
with suitable photoelectrochemical properties. The car- tionalized with [Ru(dcbH2 )2 (CNpy)(H2 O)]2+ and other
boxylic groups provide for strong adsorption of the dye to dye species has shown a linear correlation between the
the TiO2 surface and the necessary electronic coupling be- quenching efficiency, η, and the IPCE parameters.
A.S. Polo et al. / Coordination Chemistry Reviews 248 (2004) 1343–1361 1353

80

60
IPCE / %

40

20

0
390 450 510 570 630 690 750
Wavelength / nm

Fig. 3. Photocurrent action spectra of solar cells employing [Ru(dcbH2 )2 (ppy)(H2 O)]2+ (䊉), [Ru(dcbH2 )2 (ppy)2 ]2+ (䊊), [Ru(dcbH2 )2 (isq)2 ]2+ (), and
[Ru(dcbH2 )2 (CNpy)(H2 O)]2+ (䊏) as TiO2 sensitizers.

4.1.2. Non-carboxylic acid anchoring group ruthenium 4.1.3. Other d 6 complexes

complexes Most of the work in dye-sensitized solar cells has focused
Several reports have already discussed the results ob- on Ru(II) polypyridine complexes mainly because of their
tained for ruthenium complexes having non-carboxylic acid intense charge transfer absorption across the whole visible
anchoring groups, such as phosphonic acids, catechol, etc. range and ease of tunability of redox properties. Research
[88,120–124]. has also been extended to other charge transfer d6 complexes
Spectroscopic parameters and performance data for such as Fe(II) [133,134], Re(I) [135] and Os(II) [136,137].
ruthenium complexes with non-carboxylic acid anchoring Their spectroscopic and photoelectrochemical data are listed
polypyridines, in dye-sensitized solar cells, are listed in in Tables 6 and 7, respectively.
Tables 4 and 5, respectively. In recent studies, osmium complexes have also been
The phosphonic acid group has been the more investi- found to be efficient photosensitizers in nanocrystalline
gated groups among those studied for anchoring photosen- TiO2 -based solar cells [136,137]. Osmium polypyridine
sitizers onto TiO2 [88,120,123,124], as an alternative to car- complexes appear to be promising candidates for further
boxylic acid residues. The best performance was obtained optimization due to some potential advantages relative to
with phosphonic terpyridine complexes with IPCE values up their Ru analogues, as shown by impressive results with the
to 70%; these appear to be promising candidates to compete dcbH2 chromophoric ligand Os(II) complexes [136,137].
with carboxylated analogous [130]. Further modifications Replacement of the ruthenium metal center with osmium
on the phosphonated-terpy ligand, made by introducing a extends the light absorption and spectroscopic response
phenyl group close to the attaching group, provided an even of nanocrystalline TiO2 photoanode to higher wavelength
better complex to sensitize TiO2 with an IPCE as high as values without reducing photoelectrochemical energy con-
75.6%.
Recently, a new class of complexes, cis-[Ru(dobH2 )2 L2 ],
where L = Cl− or H2 O, having the hydroxamic acid,
dobH2 = 4,4 -(CONHOH)2 -2,2 -bipyridine, as an anchor-
ing group (Fig. 4) has been synthesized [43]. These new
photosensitizers exhibit intense, broad MLCT absorption,
covering a wide range of visible light. Solar cells sensi-
tized by these complexes resulted in Isc = 4.58 mA cm−2 ,
Voc = 0.595 V and ff = 0.56 for cis-[Ru(dobH2 )2 Cl2 ] and
in Isc = 4.36 mA cm−2 , Voc = 0.612 V and ff = 0.59 for
cis-[Ru(dobH2 )2 (H2 O)2 ]2+ . The data clearly point out that
these new dyes are strongly adsorbed to the mesoporous
TiO2 and promote efficient electron injection to the semi- Fig. 4. Schematic representation of the hydroxamic acid anchoring group
conductor conduction band upon light absorption. complexes, cis-[Ru(dobH2 )2 L2 ], attached on TiO2 .
1354 A.S. Polo et al. / Coordination Chemistry Reviews 248 (2004) 1343–1361

Table 4
Spectroscopic parameters for ruthenium photosensitizers with non-carboxylic acid anchoring group ligands
Complex Solvent λmax (nm) (εmax (104 M−1 cm−1 )) Reference

cis-[Ru(dobH2 )(H2 O)2 ] DMF 393, 561 [44]

cis-[Ru(dobH2 )Cl2 ] DMF 405, 576 [44]
Ru(bpy-(PO3 Et2 )2 )2 Cl2 H2 O a 308 (1.99), 379 (0.41), 528 (0.44) [125]
Ru(bpy-(PO3 H2 )2 )2 CN2 H2 O a 245 (1.2), 297 (3.12), 453 (0.56) [125]
Ru(5,5 -bpy-(PO3 H2 )2 )2 CN2 H2 O a 250 (1.97), 293 (5.53), 461 (0.454) [125]
Ru(bpy-(PO3 H2 )2 )2 NCS2 H2 O a 303 (3.396), 360 (0.786), 494 (0.7) [125]
Ru(5,5 -bpy-(PO3 H2 )2 )2 NCS2 H2 O a 250 (2.446), 299 (5.523), 351 (0.59), 515 (0.473) [125]
Ru(detOq)(NCS)2 DMF 658 (0.98), 613 (1.10), 488 (1.43), 360 (2.89), 289 (4.67) [126]
[Ru(bpy)2 (pySH)2 ] EtOH 246 (1.2), 297 (1.8), 423 (3.9) [127]
[Ru(bpy)2 (pySH)2 /ZnO 460
[Ru(bpy)2 (pyS− )] EtOH 249 (3.4), 296 (3.7) [127]
[Ru(bpy)2 (pyS− )]/ZnO 440
[(bpy)2 Ru(dpq(OH)2 )]2+ AN 252 (3.5), 286 (8.78) 453 (1.56) [128]
Ru(dsbpy)3 Cl2 H2 O 297 (8.71), 330 (1.58), 458 (1.70) [88]
Ru(dmbpy)2 (dsbpy)Cl2 EtOH 287 (8.32), 463 (1.58) [88]
Ru(dsbpy)2 Cl2 EtOH 296 (3.80), 379 (1.12), 551 (0.69) [88]
Ru(dsbpy)2 (NCS)2 EtOH 303 (3.55), 367 (1.02), 523 (1.0) [88]
[Ru(bpy)2 (bpy-CH2 COOLi)](PF6 )2 AN 456 (1.846) [124]
[Ru(bpy)2 (bpy-CH(COOLi)2 )](PF6 )2 AN 456 (1.920) [124]
[Ru(bpy)2 (bpy-(CH(COOLi)2 )2 )](PF6 )2 AN 456 (1.750) [124]
[Ru(bpy)2 (bpy-(PO3 H2 )2 )]2+ AN 456 [122]
[Ru(bpy)2 (pbp-pra)]2+ AN 458 [122]
[Ru(bpy)(bpb-pra)]2+ AN 458 [122]
[Ru(dmbpy)(DMSO)2 ]Cl2 EtOH 288 (0.94) 364 (0.21) [109]
[Ru(ttp-PO3 H2 )(dmbpy)(NCS)] EtOH 503 (0.898) [121]
[Ru(ttp-PO3 H2 )(phen)(NCS)] EtOH 497 (0.992) [121]
[Ru(ttp-PO3 H2 )(biquin)(NCS)] EtOH 572 (1.014) [121]
Ru(bmipy)(bpy-PO3 H2 )(NCS) MeOH 298 (4.46), 316 (2.44), 344 (2.98), 360 (3.70), 496 (1.13) [129]
[Ru(hp-terpy)(dmbpy)(NCS)] EtOH 494 (0.87) [130]
Ru(dmbpy)2 (bpy-acac)(PF6 )2 CH2 Cl2 462 (1.22) [131]
Bibliography since 1996.
a 0.1N H SO .
2 4

version performance. Thus the performance of solar cells much smaller than those with Ru(II) complex sensitizers,
might be improved through the use of charge transfer sensi- [Fe(dcbH2 )2 (CN)2 ] exhibits relatively high quantum yield
tizers with high spin-orbit coupling constant metal centers. for the sensitization of nanocrystalline TiO2 . As iron is a
In these systems, direct population of low-energy 3 MLCT common and cheap metal, it can provide a very economical
states is less forbidden, allowing an intensity increase of alternative to ruthenium in sensitizing complexes [134].
the corresponding charge transfer bands at the limit of the
visible-near infrared regions [1]. 4.2. Natural sensitizers
Although rhenium polypyridine compounds are not well
optimized for the harvesting of sunlight, these compounds Fruits, flowers or leaves have been employed as sources
may serve as useful probes for interfacial electron transfer of natural photosensitizers. Several reports, which are also
processes due to their interesting redox, geometric and opti- suitable for educational purposes [42,43,139,140], have em-
cal properties. The characteristic Re(II/I) reduction potential phasized the use of extracts of these sources as a faster,
provides a larger driving force for donor oxidation. The fa- cheaper, low-energy and environmentally friendly alterna-
cial geometry typical for Re(I) tricarbonyl complexes may tive for production of dye-sensitized solar cells [41–43,138].
provide a better molecular control of the orientation of the Natural dyes reported as sensitizers of solar cells are listed
dye. Lower IPCE values for [Re(CO)3 (dcbH2 )(py)]TFMS with their spectroscopic data in Table 8 and their perfor-
and [Re(CO)3 (bpy)(isn)]TFMS in comparison to analogous mance in solar cells in Table 9.
Ru(II) complexes are due to the larger fraction of light trans- Anthocyanins, which can be found easily in strongly
mitted, although the absorbed photon-to-current efficiency colored fruits, such as berries or plums as well as flow-
(APCE) is unity within experimental error. ers, are the natural dyes most extensively investigated
The [Fe(dcbH2 )2 (CN)2 ] complex can sensitize nanocrys- as photosensitizers. The strongly colored extracts have
talline TiO2 in a dye-sensitized solar cell with Voc = 0.360 V, high concentrations of anthocyanins, mainly cyanidine
Isc = 0.29 mA cm−2 and IPCE around 10–11% [133]. Al- (Fig. 5) and its derivatives, such as cyanidin-3-glucoside
though, the reported photocurrents and photovoltages were and cyanidin-3,5-diglucoside [41–43,139–141,143].
A.S. Polo et al. / Coordination Chemistry Reviews 248 (2004) 1343–1361 1355

Table 5
Photoelectrochemical data obtained with ruthenium photosensitizer with non-carboxylic acid anchoring group ligands
Dye Voc (V) Isc (mA cm−2 ) IPCEmax (%) ff ηcell (%) Reference

cis-[Ru(dobH2 )(H2 O)2 ] 0.612 4.36 0.59 [44]

cis-[Ru(dobH2 )Cl2 ] 0.595 4.58 0.56 [44]
Ru(bpy-(PO3 H2 )2 )2 Cl2 ∼20 [125]
Ru(bpy-(PO3 H2 )2 )2 CN2 ∼50 [125]
Ru(5,5 -bpy-(PO3 H2 )2 )2 CN2 ∼65 [125]
Ru(bpy-(PO3 H2 )2 )2 NCN2 0.490 5 ∼75 0.67 [125]
Ru(5,5 -bpy-(PO3 H2 )2 )2 NCN2 ∼45 [125]
[Ru(detOq)(NCS)2 ] 0.654 ± 0.050 18 ± 0.5 ∼75 0.65 ± 0.05 [126]
[Ru(bpy)2 (pySH)2 ]/ZnO 0.019 0.036 2.9 [127]
[Ru(bpy)2 (pyS− )2 ]/ZnO 0.0321 0.045 5.6 [127]
[(bpy)2 Ru(dpq(OH)2 )]2+ ∼17.5 [128]
Ru(bpy)2 (NCS)2 0.360 1.2 0.51 0.34 [132]
Ru(bpy-(NO2 )2 )2 (NCS)2 0.024 0.056 [132]
Ru(bpy-(CO2 Et)2 )2 (NCS)2 0.380 1.8 0.47 0.5 [132]
Ru(bpy-(CH2 OH)2 )2 (NCS)2 0.510 10 0.48 3.8 [132]
Ru(dsbpy)3 Cl2 0.52 1.4 0.34 0.9 [88]
Ru(dmbpy)2 (dsbpy)Cl2 0.53 1.3 0.37 0.9 [88]
Ru(dsbpy)2 Cl2 0.51 1.3 0.42 1.1 [88]
Ru(dsbpy)2 (NCS)2 0.52 0.5 0.36 0.4 [88]
[Ru(dhpt)(NCS)3 ]− 0.617 3.25 20 0.75 1.5 [123]
[Ru(bpy)2 (bpy-CH2 COOLi)](PF6 )2 0.245 0.83 34 ± 5 [124]
[Ru(bpy)2 (bpy-CH(COOLi)2 )](PF6 )2 0.400 2.55 45 ± 5 [124]
[Ru(bpy)2 (bpy-(CH(COOLi)2 )2 )](PF6 )2 0.380 3.00 48 ± 5 [124]
[Ru(bpy)2 (bpy-(PO3 H2 )2 )]2+ 0.23 ± 0.05 [122]
[Ru(bpy)2 (pbp-pra)]2+ 0.02 ± 0.01 [122]
[Ru(bpy)(bpb-pra)]2+ <0.001 [122]
[Ru(bpy)2 (phendione)]PF6 34 [120]
[Ru(bpy)2 (phendioxime)](PF6 )2 27 [120]
[Ru(ttp-PO3 H2 )(dmbpy)(NCS)] 0.653 4.73 75.6 0.705 [121]
[Ru(ttp-PO3 H2 )(phen)(NCS)] 0.625 1.88 45.4 0.814 [121]
[Ru(ttp-PO3 H2 )(biquin)(NCS)] 0.445 0.368 1.74 0.750 [121]
Ru(bmipy)(bpy-PO3 H2 )(NCS) 0.60 8.6 55 0.70 4.1 [129]
[Ru(hp-terpy)(dmbpy)(NCS)] ∼70 [130]
[Ru(dmbpy)2 (bpy-acac)](PF6 )2 0.487 2.02 0.292 [131]
Bibliography since 1996.

Table 6
Spectroscopic parameters of other d6 metal complexes evaluated as photosensitizers
Complex Solvent λmax (nm) (εmax (104 M−1 cm−1 )) Reference

Os(dcbH2 )2 (CN)2 EtOHa 382 (1.40), 508 (1.44), ∼680 (0.368) [136]
Os(dcbH2 )2 (NCS)2 EtOH 412 (1.43), 530 (1.51), ∼780 (0.5) [136]
[Os(dcbH2 )2 Cl2 ]2+ EtOH 448 (1.68), 494 (1.48), ∼640 (0.4) [136]
[Os(dcbH2 )3 ]2+ EtOH 442 (1.01), 496 (2.02), ∼640 (0.6) [136]
TBA4 [Fe(dcbH2 )2 (CN)2 ] EtOH 590 [134]
3-MPN 594 [134]
CCl4 595 [134]
DMSO 621 [134]
TBA4 [Fe(dcbH2 )2 (CN)2 ]/TiO2 EtOH 610 [134]
3-MPN 608 [134]
CCl4 596 [134]
DMSO 638 [134]
[Re(CO)3 (dcbH2 )(py)]TFMS AN 380 (0.44) [135]
[Re(CO)3 (bpy)(isn)]TFMS AN 350 (0.53) [135]
Bibliography since 1998.
a In EtOH with 1 mM pyridine and 1 mM pyridinium triflate.
1356 A.S. Polo et al. / Coordination Chemistry Reviews 248 (2004) 1343–1361

Table 7
Photoelectrochemical data obtained with solar cell sensitized by other d6 metal complexes
Dye Voc (V) Isc (mA cm−2 ) IPCEmax (%) ff Reference

Os(dcbH2 )2 (CN)2 0.569 11.6 0.62 [136]

Os(dcbH2 )2 (NCS)2 0.360 2.1 0.55 [136]
[Os(dcbH2 )2 Cl2 ]2+ 0.540 7.7 0.66 [136]
[Os(dcbH2 )3 ]2+ 0.514 10.0 0.69 [136]
TBA4 [Fe(dcbH2 )2 (CN)2 ] 0.360 0.29 10–11 [133]
[Re(CO)3 (dcbH2 )(py)]TFMS ∼0.9 [135]
[Re(CO)3 (bpy)(isn)]TFMS ∼0.5 [135]
Bibliography since 1998.

The maximum absorption of anthocyanin extracts ranges droxyl groups present at the TiO2 nanostructured surface,
from 510 to 548 nm depending on the fruit or the solvent as shown in Fig. 5a. The attachment can also be enhanced
employed. In most cases bathochromic shifts are observed by a chelating contribution to the Ti(IV) ions, Fig. 5b
after attachment to the semiconductor (Fig. 6). Chemical [142].
adsorption of the anthocyanins is stated to be the result Dai and Rabani in their studies with pomegranate ex-
of its alcohol bound protons which condense with the hy- tracts reported the successful use of an aqueous mediator
layer [142]. Another interesting behavior has been observed
with gallic acid and catechol. These compounds do not
Table 8 present charge transfer transitions bands in solution, how-
Spectroscopic parameters of natural extracts evaluated as photosensitizers
since 1997
ever after their adsorption onto semiconductor surface they
present a strong absorption band. This behavior is due to the
Extract of Medium λmax Reference
(nm)
chelating effect enhancing their binding onto TiO2 surface
[146].
Jaboticaba’s skin EtOH 538 [43]
Most natural dye-sensitized solar cells have been evalu-
TiO2 548 [43] ated by short circuit current, Isc , and open circuit voltage,
Voc , measurements as can be observed in Table 9.

Chaste tree fruit EtOH 548 [41]

TiO2 555 [41]
TiO2
TiO2

O O
Mulberry EtOH 543 [41] O O
TiO2 553 [41]
O OH O OH

HO HO
Cabbage-palm fruit EtOH 545 [41] (a) OH (b) OH
TiO2 552 [41]
Fig. 5. Schematic representation of anthocyanin attachments onto TiO2
surface.

Java Plum EtOH 536 [42,43]

TiO2 550 [42,43]

Blackberries H2 O 517 [141]

California Blackberries MeOH/ 520a [143]
HOAc/H2 O
TiO2 532 [143]
Pomegranate seeds TiO2 560 [142]
H2 O 510–520 [142]
Pomegranate fruit H2 O 520 [138]
TiO2 560 [138]
Fig. 6. Absorption spectra of an ethanolic extract of Jaboticaba’s skin
a Molar absorptivity = 3.5 × 104 L mol−1 cm−1 [144]. before (– – –) and after being adsorbed onto TiO2 surface (—).
A.S. Polo et al. / Coordination Chemistry Reviews 248 (2004) 1343–1361 1357

Table 9
Photoelectrochemical data obtained with solar cell sensitized by anthocyanin natural extracts evaluated as photosensitizers
Extract of Mediuma Voc (V) Isc (mA cm−2 ) Reference

Jaboticaba’s skin AN/NMO 0.59 2.8 [43]

Chaste tree fruit AN/NMO 0.39 2.1 [41]
Mulberry AN/NMO 0.42 1.7 [41]
Cabbage-palm fruit AN/NMO 0.44 0.74 [41]
Java Plum AN/NMO 0.71 4.6 [42]
Blackberries, raspberries, pomegranate seeds EG 0.3–0.5 1–2 [139]
Blackberries, raspberries, pomegranate seeds EG 0.3–0.5 1–2 [140]
Blackberries 0.30 1 [141]
California Blackberriesb EG or PC 0.4–0.5 1.5–2.2 [143]
California Blackberriesb EG or PC 0.4–0.43 1–1.2 [143]
Pomegranate fruit H2 O pH 2.8 0.30–0.44 0.45–2.2 [142]
EtOH 0.41, 0.48 2.1, 0.48 [142]
Pomegranate fruit H2 O 0.46 [142]
Pomegranate fruit H2 O 0.45 [138]
Anthurium H2 O 0.435 2.9 [145]
AN 0.480 3.2 [145]
Bibliography since 1997.
a Electrolyte I − /I− .
3
b The extract was purified to obtain only anthocyanin compounds.

Anthocyanin photosensitizers usually exhibit a photovolt- group to analyze the feasibility of using the extracts of
age between 0.3 and 0.71 V and photocurrent values ranging plants widely spread over the Brazilian territory. The re-
from 0.45 and 4.6 mA cm−2 . However, few studies have in- sults obtained with Java Plum (Eugenia jambolana Lam),
cluded the overall efficiency, which ranges from 0.5 to 1% Jaboticaba’s skin (Mirtus cauliflora Mart), cabbage-palm
[139,140,143], and IPCE value up to 19% at the maximum fruit (Euterpe oleracea Mart), among others, have already
absorbance [143]. proved the possibility of using these common Brazilian
The performance of natural extracts are usually better fruits as alternative dye sources. For instance, an outstand-
than those obtained by using commercial or purified analo- ing Isc = 2.8 mA cm−2 and Voc = 0.59 V, as well as fill fac-
gous compounds. The improved natural dye performance is tor of 0.48, obtained from the current-voltage profile shown
probably due to a mixture of dyes present in such extracts in Fig. 7, for extract of Jaboticaba’s skin, have encour-
[138]. Different dyes promote light harvesting in distinct aged us to continue searching for new natural dyes sources
wavelengths and have particular electron injection quantum [41–43].
yields leading to the enhancement of photocurrent and pho-
tovoltage [142].
The great biodiversity found in Brazil, with special em- 5. Closing remarks
phasis in the Amazon and Northeast regions, has led our
The dye-sensitized solar cell is considered the new gen-
eration solar cell for the 21st century and is a fast growing
-3.0 multidisciplinary subject. Since its first announcement in
1991, using the concept of chemisorbed dye on the sur-
-2.5 face of mesoporous TiO2 photoelectrode with a roughness
ff = 0.48
factor of 1000, the efficiency has increased from the ini-
-2.0
Jsc /m Ac m-2

tial 7.1% to a presently certified efficiency of over 10%

-1.5 under standard AM 1.5 solar radiation. Increasing stability
and improvements on manufacturing techniques, as well
-1.0 as the announcement of the commercial production should
direct investments by several companies in this renew-
-0.5 able energy technology in their search for a clean energy
business.
0.0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 A photoelectrochemical solar cell based on the dye-
sensitization of n-TiO2 represents an example of an in-
V / Volts tegrated chemical system for energy conversion. The
Fig. 7. Current–potential curve for solar cells incorporating a photoanode sensitization of a wide band gap semiconductor oxide
sensitized by extract of Jaboticaba’s skin. film of nanocrystalline morphology, stable against pho-
1358 A.S. Polo et al. / Coordination Chemistry Reviews 248 (2004) 1343–1361

tocorrosion, allows the efficient harvesting of sunlight properties conveniently in order to better absorb visible light
with near quantitative conversion of incident photons into to be converted into electrical output. Recent papers of our
current. group also reported successful use of extract of Brazilian
fruits as a natural sensitizer in photoelectrochemical solar
5.1. Work on Dye-cell at the IQ/USP, Brazil cells [40–43].
Conducting plastic materials have also been tested to re-
At the Laboratory of Inorganic Photochemistry and En- place a rigid TCO as the electrode substrate in association
ergy Conversion in the Chemistry Institute of the University with a polymeric gel as an electrolyte medium resulting in
of São Paulo (IQ/USP), we are working on several aspects wholly flexible solar cells [147].
related to the Dye-cell technology, including developing the The development of solar cells became the main subject
pathway from fundamental academic scientific knowledge of a special program called CIUPE (Inter-institutional Col-
acquired from research to technological innovation and in- laborative Program for Strategic Researches), which was
tellectual protection by patents. A straightforward example supported by the University of São Paulo and attracted re-
of the association of both molecularly engineered chemical searchers from several areas. It involved mainly discussions
systems and photoinduced tasks for energy conversion is on subjects related with renewable energy sources and the
represented by our results with the photoelectrochemical development of photovoltaics and has provided encourage-
solar cell based on dye-sensitization of n-TiO2 . Compounds ment for cooperative efforts among several different labora-
with the general formula cis-[Ru(dcbH2 )2 LL ] (Fig. 2) tories [5].
where L/L = substituted pyridines and H2 O, were suc- Our project “Dye-sensitized solar cells: Dye-cells” al-
cessfully employed as molecular sensitizers in such cells ready has three patents and has been select by the Brazilian
[36–38]. Ministry of Science and Technology (MCT) as an innovative
Preparation of colloidal TiO2 using distinct methods has project/product in the energy sector, and took part during
also been tested giving reliable and very useful results. the whole year of 2002 in a series of events entitled “Ex-
Spin-coating and painting techniques have been employed hibition of Innovative Technological Products for Energy
for the deposition of TiO2 films over TCO substrates. Production”. As a result several companies have contacted
Homogeneous semiconductor films with controlled trans- us and showed interest in the Dye-cell as the photovoltaic
parency, which were successfully used as dye-sensitized technology for the New Millennium.
photoanodes in solar cells, have been obtained with the con- Although ascending, the development of photovoltaic so-
venient choice of TiO2 preparation techniques. Thin-film lar energy in Brazil is considerably recent and its contribu-
properties, such as thickness and transparency, were also tion as an alternate energy source is still incipient. However,
controlled through the deposition technique [5]. due to its geographic characteristics, large territorial area, fa-
The electron transfer process across the excited dye/ vorable tropical climate and the existence of several remote
semiconductor interface, as well as the charge recombina- communities not provided with an electrical energy network,
tion and quenching processes, were further investigated by photovoltaics is the most feasible alternative, when the envi-
transient UV–vis absorption spectra on dye-sensitized TiO2 ronmental and the resources conservation are considered, to
films deposited onto glass substrates. A fast quenching of solve at least some of these specific Brazilian energy needs.
the oxidized complex in the presence of iodide emphasized
the importance of a proper concentration of donor species
in the redox mediator for the effective regeneration of the Acknowledgements
oxidized sensitizer [39,119].
Molecular engineering of the cis-[Ru(dcbH2 )2 LL ] com- The authors are grateful to Dr. Christian Graziani Gar-
pounds, with different L,L ancillary ligands, that fulfill sev- cia, Karina Passalacqua Morelli Frin and Fernando Mendes
eral requirements and act as panchromatic charge transfer de Oliveira for the valuable assistance. Financial support
sensitizers for wide band gap semiconductor solar cells is of the Conselho Nacional de Desenvolvimento Cientı́fico e
still a challenging task, but in continuous study. Our investi- Tecnológico, CNPq, the Fundação de Amparo à Pesquisa
gation efforts now progress also towards the development of do Estado de São Paulo, FAPESP and the Fundo Bunka
new synthetic dyes and to the discovery of natural dyes to be de Pesquisa-Banco Sumitomo Mitsui are acknowledged. We
efficiently used as semiconductor sensitizers. Sunlight har- also thank Asahi Glass Co. for the supply of TCO.
vesting and energy conversion to electricity assisted by a new
class of complexes, cis-[Ru(dobH2 )2 LL ], having two hy-
droxamic acid groups as an anchoring site to be attached on References
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