Density Functional Study of Metal-to-Ligand Charge Transfer and Hole-Hopping in Ruthenium(II) Complexes with Alkyl-Substituted Bipyridine Ligands

[Image: see text] In this study, we present a density functional study of four ruthenium complexes by means of UV–visible spectroscopy and Marcus theory. These molecules, [Ru(II)(bipyP)(bipy)(2)] (P1), [Ru(II)(bipyP)(dmb)(2)] (P2), [Ru(II)(bipyP)(dtbb)(2)] (P3), and [Ru(II)(bipyP)(dnb)(2)] (P4), where bipyP = 2,2′-bipyridine-4,4′-diphosphonic acid, bipy = 2,2′-bipyridine, dmb = 4,4′-dimethyl-2,2′-bipyridine, dtbb = 4,4′-di-tert-butyl-2,2′-bipyridine, and dnb = 4,4′-dinonyl-2,2′-bipyridine, are photosensitizers for applications in dye-sensitized photo-electrochemical cells (DSPECs). Because of the undetermined P4 conformation in the experiment, we modeled three P4 conformers with straight (P4-straight) and bent nonyl chains (P4-bend1 and bend2). UV–vis absorption spectra by time-dependent density functional theory showed intense metal-to-ligand charge transfer to anchor bipyridine ligands (MLCT-anchoring) at 445–460 nm, which accurately reproduce experimental data. The largest light-harvesting efficiency of the MLCT-anchoring state was observed in the P4-bend1 conformer, which has the lowest P4 energy. This may relate to greater electron injection in the P4 and supports experimental results of dye-only systems (do-DSPEC). The calculated charge transfer rates agree well with the experimental trend. The largest rate was obtained for P2, which was attributed to the expansion of the highest-occupied molecular orbital toward the ancillary bipy ligands and also to the short distances between dyes on the TiO(2) surface. These results also support experimental results for P2, which was the best compound for lateral hole-hopping in a sacrificial agent-containing system (sa-DSPEC).