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Dye-sensitized photoelectrodes may be used as heterogeneous components for fuel-forming reactions in photoelectrochemical cells. There has been increasing interest in developing Earth-abundant cheaper photosensitizers based on first-row transition metals. We describe here the synthesis, characterization, and study of the ground and excited state properties of three Cu(I) complexes bearing ligands with varying electron-accepting capacities and conjugation that may act as photosensitizers for wide bandgap semiconductors. Femtosecond transient absorption studies indicate that the nature of the final excited state is dictated by the extent of conjugation in the electron-accepting ligand, where shorter conjugation leads to the formation of a singly reduced ligand and longer conjugation leads to the formation of a ligand-centered final excited state. These complexes were surface anchored onto nanostructured NiO on conductive fluorine-doped tin oxide glass to fabricate photocathodes. It was found that even though the ligands with increasing conjugation have an effect on the formation of the final excited state in solution, all complexes exhibit similar photocurrents upon white light illumination, suggesting that charge transfer to NiO happens in advance of the formation of the final excited state.