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Ligand Rigidity Steers the Selectivity and Efficiency of the Photosubstitution Reaction of Strained Ruthenium Polypyridyl Complexes

Title	Ligand Rigidity Steers the Selectivity and Efficiency of the Photosubstitution Reaction of Strained Ruthenium Polypyridyl Complexes
Authors	Matthijs L. A. Hakkennes, Michael S. Meijer, Jan Paul Menzel, Anne-Charlotte Goetz, Roy Van Duijn, Maxime A. Siegler, Francesco Buda, Sylvestre Bonnet
Magazine	Journal of the American Chemical Society
Date	06/09/2023
DOI	10.1021/jacs.3c03543
Introduction	Photosubstitution reactions in metal complexes, traditionally regarded as dissociative and environment-insensitive, are actually significantly influenced by solvent interactions. This study investigates the photosubstitution selectivity of diimine chelates in a range of sterically strained ruthenium(II) polypyridyl complexes using both experimental and computational approaches in water and acetonitrile environments. The rigidity of the chelates proved to be a crucial factor affecting photosubstitution selectivity. The impact of the solvent was evident in modifying photoproduct ratios, leading to the creation of a density functional theory model that incorporates explicit solvent molecules. We identified three distinct reaction pathways on the triplet hypersurface, each with specific energy barriers. In water, photodissociation was promoted by proton transfer in the triplet state, facilitated by a dissociated pyridine ring acting as a pendent base. Temperature-dependent changes in photosubstitution quantum yield were instrumental in aligning theoretical predictions with experimental results. Importantly, in acetonitrile, an unusual reduction in the rate of photosubstitution was observed with increasing temperatures. This was explained by mapping the triplet hypersurface, which revealed thermal deactivation to the singlet ground state via intersystem crossing.
Quote	Matthijs L. A. Hakkennes, Michael S. Meijer and Jan Paul Menzel et al. Ligand Rigidity Steers the Selectivity and Efficiency of the Photosubstitution Reaction of Strained Ruthenium Polypyridyl Complexes. J. Am. Chem. Soc. 2023. Vol. 145(24):13420-13434. DOI: 10.1021/jacs.3c03543
Element	Ruthenium (Ru)
Industry	Chemical & Pharmacy

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