Substitution‐Controlled Excited State Processes in Heteroleptic Copper(I) Photosensitizers Used in Hydrogen Evolving Systems

Four different heteroleptic [Cu(N^N)(P^P)]PF6 complexes, which combine classical bidentate diimine ligands and sterically demanding diphosphine ligands, are studied by a combination of ultrafast time-resolved spectroscopy and quantum chemical calculations. The light-induced excited state processes, accompanied by a structural change, are discussed with respect to the application of these complexes as a new class of noble-metal-free photosensitizers in proton reducing systems. In particular, the influence of different substituents in the ligand backbone on the photophysical properties is highlighted.