Photocatalysis: The photophysical properties of a series of RuII based photocatalysts are investigated by means of quantum chemical methods. Through selective co-ligand design, greater control can be exerted over the electron transfer pathways, targeted at increasing electron localisation on the bridging ligand and reducing deactivation through 3MC states.
Quantum chemical methods have been utilised to explore the kinetics and thermodynamics of a prominent charge recombination pathway in a series of RuII based molecular photocatalysts. Selective tuning of the RuII coordination sphere, replacing the tbbpy ligands of the hydrogen evolving parent photocatalyst with electron rich, biimidazole based ligands, promotes unidirectional charge transfer towards the bridging ligand during initial photoexcitation. These electronic effects are also significant in the triplet manifold, where the predicted rate of the undesired deactivation process from the 3MLCT state on the bridging ligand to a 3MC state on the ruthenium centre, is decreased relative to the parent complex, by 1–2 orders of magnitude, alongside a decrease in electronic coupling. This design methodology could be utilised to promote targeted (light-driven) electron transfer pathways, as well as to potentially reduce 3MC deactivation pathways in commonly used polypyridyl-based RuII photocentres, thus enhancing the quantum efficiency of light driven catalysis.Zum Volltext