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Three new tris-heteroleptic complexes of ruthenium(II) were designed by coordinating the metal center with cyclometalating, anchoring, and auxiliary ligands with different donor substituents. N-Hexylcarbazole, N-hexylphenothiazine, and N-hexyldiphenylamine donor moieties were used as substituents on the auxiliary ligands for SA633, SA634, and SA635, respectively. Complexes were characterized by 1H and 13C 2D-COSY NMR techniques. These complexes provide power conversion efficiencies in the range of 7.6–8.2% when they are employed in state of the art dye-sensitized solar cells (DSCs) with cobalt electrolyte. Various electrochemical and transient techniques were used to unveil the unexpected differences in the performance of these very similar sensitizers.

We report a blue dye, coded as R6, which features a polycyclic aromatic hydrocarbon, 9,19-dihydrobenzo[1′,10′]phenanthro[3′,4′:4,5]thieno[3,2-b]benzo[1,10]phenanthro[3,4-d]thiophene, coupled with a diarylamine electron donor and 4-(7-ethynylbenzo[c][1,2,5]thiadiazol-4-yl)benzoic acid acceptor. Dye R6 displays a brilliant sapphire color in a sensitized TiO2mesoporous film with a Co(II/III) tris(bipyridyl)-based redox electrolyte. The R6 based dye-sensitized solar cell achieves an impressive power conversion efficiency of 12.6% under standard air mass 1.5 global, 100 mW cm–2, and shows a remarkable photostability.