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 H-1 and C-13 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.