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Comprehensive Characterization of the Electronic Structure of U(4+) in Uranium(IV) Phosphate Chloride.
Inorganic Chemistry 2016 July 19
Emerald-green single crystals of U(PO4)Cl were grown by chemical vapor transport in a temperature gradient (1000 → 900 °C). The crystal structure of U(PO4)Cl (Cmcm, Z = 4, a = 5.2289(7) Å, b = 11.709(2) Å, c = 6.9991(8) Å) consists of a three-dimensional network of [PO4] tetrahedra and bicapped octahedral [U(IV)O6Cl2] groups. Polarized absorption spectra measured for two perpendicular polarization directions show a large number of well-resolved electronic transitions. These transitions can be fully assigned on the basis of a detailed ligand-field treatment within the framework of the angular overlap model. The magnetic behavior predicted on the basis of the spectroscopic data is in agreement with an f (2) system and perfectly matched by the results of temperature-dependent susceptibility measurements.
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