Physical Chemistry Chemical Physics vol:6 issue:13 pages:3292-3298
The complex formation of uranyl with chloride ions in non-aqueous solvents (acetone, tributylphosphate and methyl-i-butylketone) was studied by absorption, luminescence and MCD spectroscopy. The maximal coordination of the uranyl ion by chloride ions in these organic solvents was found to be four, which is in agreement with single crystal data. The MCD spectra unambiguously exclude the existence Of [UO2Cl3](-) with D3h coordination symmetry. For the intermediately formed complexes we propose a structure of the type: UO2Cl2(solv)(4), with an orthorhombic symmetry. For these intermediate complexes, the 19 500-22 000 cm(-1) region of the absorption spectrum exhibits an intensity enhancement with respect to that of the solvated uranyl ion. This intensity enhancement as well as the increase in total luminescence intensity is explained in terms of vibronic coupling of the first electronic state (Pi(g)) with the asymmetric stretching (nu(a):a(2u)) and the bending (nu(b):e(u)) vibrations of the uranyl ion and the out-of-plane bending mode of the equatorial ligands (nu(10):b(1u)). The spectra are dominated by transitions arising from the sigma(u)(+)delta(u) configuration. The spectroscopic properties of the UO2Cl2(TBP)(x) complexes are compared with those of the UO2(NO3)(2)(TBP)(2) complex (TBP = tributylphosphate).