Contrasting solvent and capping ligand effects directing the photochemistry of uranyl(VI) Schiff base complexes |
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Authors: | Vaughn Anthony E Bassil Daniel B Barnes Charles L Tucker Sheryl A Duval Paul B |
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Institution: | Department of Chemistry, University of Missouri-Columbia, 601 S. College Avenue, Columbia, Missouri 65211, USA. |
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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. |
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