Contrasting Solvent and Capping Ligand Effects Directing the Photochemistry of Uranyl(VI) Schiff Base Complexes

Photolysis of the uranyl(VI) Schiff base complex UO₂(^tBu₄-salphen)(THF) (1a) with cobaltocene in THF affords [Cp₂Co][UO₂(^tBu₄-salphen)(OH)] (2) in high yield while irradiation in toluene yields no reaction. Electronic emission spectra of 1a reveal a large Stokes' shift in toluene similar to that observed in the free ligand, while in THF the structural rearrangement responsible for this shift is blocked. Instead, the ligand-centered excited state is redirected to the uranyl(VI) center by way of energy transfer, thus generating 2 from the intramolecular activation of a coordinated THF molecule.