The terminal ligand in (Ph₂phen)₂Ru(dpp)RhCl₂(TL)₃ (Ph2phen = 4,7-diphenyl1,10-phenanthroline; dpp = 2,3-bis(2-pyridyl)pyrazine; TL = terminal ligand – a 4,4′-disubstituted-2,2′-bipyridine where the substituent was carbomethoxy (dcmbpy), hydrogen (bpy) or methyl (Me₂bpy)). The electron-withdrawing ability of the substituent was shown to increase the rate of chloride loss upon electrochemical reduction, facilitating catalytic water reduction. The electronic properties of the terminal ligand also impact the photophysical properties of the molecule. The excited state lifetime of the complex with a dcmbpy terminal ligand was 93 ns while the excited state lifetimes of the complexes with a bpy or Me₂bpy terminal ligand were 44 ns and 47 ns, respectively. Ligand substitution was shown to influence the photocatalytic water reduction activity of these complexes with the dcmbpy complex producing approximately twice the amount of hydrogen (62 ± 7 turnovers in 20 h) as the other two complexes.