title: Contrasting solvent and capping ligand effects directing the photochemistry of uranyl(VI) Schiff base complexes.
abstract: 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.
authors.affiliation: Department of Chemistry, University of Missouri-Columbia, 601 S. College Avenue, Columbia, Missouri 65211, USA.
authors.forename: Anthony E
authors.initials: AE
authors.lastname: Vaughn
authors.forename: Daniel B
authors.initials: DB
authors.lastname: Bassil
authors.forename: Charles L
authors.initials: CL
authors.lastname: Barnes
authors.forename: Sheryl A
authors.initials: SA
authors.lastname: Tucker
authors.forename: Paul B
authors.initials: PB
authors.lastname: Duval