Outer-sphere effects on ligand-field excited-state dynamics: solvent dependence of high-spin to low-spin conversion in [Fe(bpy)₃]².

ABSTRACT: In condensed phase chemistry, the solvent can have a significant impact on everything from yield to product distribution to mechanism. With regard to photo-induced processes, solvent effects have been well-documented for charge-transfer states wherein the redistribution of charge subsequent to light absorption couples intramolecular dynamics to the local environment of the chromophore. Ligand-field excited states are expected to be largely insensitive to such perturbations given that their electronic rearrangements are localized on the metal center and are therefore insulated from so-called outer-sphere effects by the ligands themselves. In contrast to this expectation, we document herein a nearly two-fold variation in the time constant associated with the ⁵T₂ →

SUBMITTER: Miller JN 

PROVIDER: S-EPMC8159330 | biostudies-literature | 2020 May

REPOSITORIES: biostudies-literature