Panchromatic sensitization of nanocrystalline TiO2 with cis-Bis(4-carboxy-2-[2'-(4'-carboxypyridyl)]quinoline)bis(thiocyanato-N)ruthenium(II)

We compared the spectral (IR and Raman), electrochemical, and photoelectrochemical properties of nanocrystalline TiO(2) sensitized with the newly synthesized complex NBu(4)](2)cis-Ru(Hdcpq)(2)(NCS)(2)] (1; NBu(4)](+) = tetrabutylammonium cation; H(2)dcpq = 4-carboxy-2-2'-(4'-carboxypyridyl)]quinoline) with those of TiO(2) sensitized with NBu(4)](2)cis-Ru(Hdcbpy)(2)(NCS)(2)] (2; H(2)dcbpy = 4,4'-dicarboxy-2,2'-bipyridine) and NBu(4)](2)cis-Ru(Hdcbiq)(2)(NCS)(2)] (3; H(2)dcbiq = 4,4'-dicarboxy-2,2'-biquinoline). Complex 1 achieved efficient sensitization of nanocrystalline TiO(2) films over a wide visible and near-IR region, generating a large short-circuit photocurrent. The absorbed photon-to-current conversion efficiency decreased in the order 2 > 1 > 3 with the decrease in the free energy change (-Delta G(inj)) of the electron injection from the ruthenium complex to TiO(2). The open-circuit photovoltages (V(oc)'s) of dye-sensitized solar cells decreased in the order 2 > 1 > 3 with the increase in the dark current resulting from reverse electron transfer from TiO(2) to I(3)(-). The sensitizer-dependent V(oc) value can be interpreted as a result of reverse electron transfer through the sensitizing dye molecules.