Oxidation-state sensitive light-induced dynamics of Ruthenium-4H-Imidazole complexes

Oxidized molecular states are key intermediates in photo-induced redox reactions, e. g., intermolecular charge transfer between photosensitizer and catalyst in photoredox catalysis. The stability and longevity of the oxidized photosensitizer is an important factor in optimizing the respective light-driven reaction pathways. In this work the oxidized states of ruthenium(II)-4H-imidazole dyes are studied. The ruthenium complexes constitute benchmark photosensitizers in solar energy interconversion processes with exceptional chemical stability, strong visible light absorption, and favourable redox properties. To rationalize the light-induced reaction in the oxidized ruthenium(III) systems, we combine UV-vis absorption, resonance Raman, and transient absorption spectroelectrochemistry (SEC) with time-dependent density functional theory (TDDFT) calculations. Three complexes are compared, which vary with respect to their coordination environment, i. e., combining an 4H-imidazole with either 2,2'-bipyridine (bpy) or 2,2';6'2"-terpyridine (tpy) coligands, and chloride or isothiocyanate ligands. While all oxidized complexes have similar steady state absorption properties, their excited state kinetics differ significantly; the study thus opens the doorway to study the light-driven reactivity of oxidized molecular intermediates in intermolecular charge transfer cascades.