Theoretical Investigation of the Anion Binding Affinities of the Uranyl Salophene Complexes

The uranyl salophene complex and its co-complexes with several anions (H 2 PO 4 -, HSO 4 -, NO 2 -, OH -, Cl -, F - ) in the gas phase are investigated theoretically. Equilibrium geometries of relevant species and complexation-induced structural changes are discussed. The 13 C NMR chemical shifts calculated at the gas-phase optimized geometry agree very well with experimental liquid-phase results. The optimized geometry agrees also very well with available crystallographic data. This indicates that the gas-phase structures derived from theoretical calculations can be considered representative also for the condensed phase. For all anions, except H 2 PO 4 -, the calculated gas-phase binding energies correlate well with experimental Gibbs free energies of complexation. The possible role of the solvent in the case of H 2 PO 4 - complexation is discussed.