Two novel supramolecular complexes RuRe ([Ru(dceb)₂(bpt)Re(CO)₃Cl](PF₆)) and RuPt ([Ru(dceb)₂(bpt)PtI(H₂O)](PF₆)₂) [dceb = diethyl(2,2′-bipyridine)-4,4′-dicarboxylate, bpt = 3,5-di(pyridine-2-yl)-1,2,4-triazolate] were synthesized as new catalysts for photocatalytic CO₂ reduction and H₂ evolution, respectively. The influence of the catalytic metal for successful catalysis in solution and on a NiO semiconductor was examined. IR-active handles in the form of carbonyl groups on the peripheral ligand on the photosensitiser were used to study the excited states populated, as well as the one-electron reduced intermediate species using infrared and UV-Vis spectroelectrochemistry, and time resolved infrared spectroscopy. Inclusion of ethyl-ester moieties led to a reduction in the LUMO energies on the peripheral bipyridine ligand, resulting in localization of the ³MLCT excited state on these peripheral ligands following excitation. RuPt generated hydrogen in solution and when immobilized on NiO in a photoelectrochemical (PEC) cell. RuRe was inactive as a CO₂ reduction catalyst in solution, and produced only trace amounts of CO when the photocatalyst was immobilized on NiO in a PEC cell saturated with CO₂.