Mechanistic Insights into the Oxidative and Reductive Quenching Cycles of Transition Metal Photoredox Catalysts through Effective Oxidation State Analysis.

The electronic structures of the ground and excited electronic states involved in the oxidative and reductive quenching cycles of 12 relevant ruthenium, iridium, and copper photoredox catalysts ( S 0 , T 1 , D ox , and D red ) are characterized using the recently developed effective oxidation state (EOS) analysis, allowing the monitoring of metal and ligand oxidation states (OSs) along the catalytic cycles. The formal oxidation state assignments derived from the EOS analysis are in agreement with those commonly assumed for these complexes in both ground and excited states. Rather clean and separate ligand- and metal-centered redox events along the different quenching cycles are observed in most of the studied molecular systems. The reliability index obtained for the OS assignations can be readily interpreted in terms of the ionic/covalent character of metal-ligand interactions and ligand non-innocent character. In addition, EOS analysis reveals the high-degree localization of the ligand-centered redox event to one or two redox-active ligand(s) in heteroleptic complexes. Ligand- and metal-condensed spin populations were also computed and analyzed for all the open-shell species involved in this study, showing promises for rapid oxidation state assignments in certain systems, especially Ru complexes, however, suffering from severe defects in other cases.