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

ABSTRACT: While photosubstitution reactions in metal complexes are usually thought of as dissociative processes poorly dependent on the environment, they are, in fact, very sensitive to solvent effects. Therefore, it is crucial to explicitly consider solvent molecules in theoretical models of these reactions. Here, we experimentally and computationally investigated the selectivity of the photosubstitution of diimine chelates in a series of sterically strained ruthenium(II) polypyridyl complexes in water and acetonitrile. The complexes differ essentially by the rigidity of the chelates, which strongly influenced the observed selectivity of the photosubstitution. As the ratio between the different photoproducts was also influenced by the solvent, we developed a full density functional theory modeling

SUBMITTER: Hakkennes MLA 

PROVIDER: S-EPMC10299800 | biostudies-literature | 2023 Jun

REPOSITORIES: biostudies-literature