Ruthenium sensitizers with a hexylthiophene-modified terpyridine ligand for dye-sensitized solar cells: synthesis, photo- and electrochemical properties, and adsorption behavior to the TiO2 surface.

Two novel ruthenium sensitizers with a hexylthiophene-modified terpyridine ligand (TUS-35 and TUS-36) were synthesized to improve the molar absorptivity of the previously reported ruthenium sensitizer (TBA)[Ru{4'-(3,4-dicarboxyphenyl)-4,4″-dicarboxyterpyridine}(NCS)3], TBA = tetrabutylammonium (TUS-21). A relatively strong absorption appeared at ∼380 nm, and the molar absorption coefficient at the metal-to-ligand charge transfer (MLCT) band decreased in TUS-35 by introducing a 2-hexylthiophene unit to the 5-position of the terpyridine-derived ligand. For comparison, a relatively strong absorption was observed at ∼350 nm without decreasing the molar absorption coefficient at the MLCT band in TUS-36 by introducing a 2-hexylthiophene unit to the 4-position of the terpyridine-derived ligand. On the other hand, the energy levels of the highest occupied molecular orbitals and the lowest unoccupied molecular orbitals of these two sensitizers were found to be almost equal to those of TUS-21. The adsorption behavior of TUS-35 and TUS-36 was similar to that of (TBA)[Ru{4'-(3,4-dicarboxyphenyl)terpyridine}(NCS)3] (TUS-20), which binds to the TiO2 surface by using the 3,4-dicarboxyphenly unit, rather than that of TUS-21, which adsorbs to the TiO2 photoelectrode using one of the carboxyl groups at the terminal pyridines of the terpyridine-derived ligand. Therefore, TUS-35 and TUS-36 are considered to bind to the TiO2 surface by using the 3,4-dicarboxyphenly unit just like TUS-20. The dye-sensitized solar cells (DSCs) with TUS-35 and TUS-36 showed a relatively lower conversion efficiency (6.4% and 5.7%, respectively) compared to the DSC with TUS-21 (10.2%). Open-circuit photovoltage decay and electrochemical impedance spectroscopy measurements revealed that the promoted charge recombination and/or charge transfer of the injected electrons in the TiO2 photoelectrode is a main reason for the inferior performances of TUS-35 and TUS-36.