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

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 (5)T(2) → (1)A(1) high-spin to low-spin relaxation process of tris(2,2′-bipyridine)iron(ii) ([Fe(bpy)(3)](2+)) across a range of different solvents. Likely origins for this solvent dependence, including relevant solvent properties, ion pairing, and changes in solvation energy, were considered and assessed by studying [Fe(bpy)(3)](2+) and related derivatives via ultrafast time-resolved absorption spectroscopy and computational analyses. It was concluded that the effect is most likely associated with the volume change of the chromophore arising from the interconfigurational nature of the (5)T(2) → (1)A(1) relaxation process, resulting in changes to the solvent–solvent and/or solvent–solute interactions of the primary solvation shell sufficient to alter the overall reorganization energy of the system and influencing the kinetics of ground-state recovery.