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

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posted on 23.08.2006, 00:00 authored by Anthony E. Vaughn, Daniel B. Bassil, Charles L. Barnes, Sheryl A. Tucker, Paul B. Duval
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.