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  • Title: Structure and bonding of the vanadium(III) hexa-aqua cation. 1. Experimental characterization and ligand-field analysis.
    Author: Tregenna-Piggott PL, Spichiger D, Carver G, Frey B, Meier R, Weihe H, Cowan JA, McIntyre GJ, Zahn G, Barra AL.
    Journal: Inorg Chem; 2004 Dec 13; 43(25):8049-60. PubMed ID: 15578844.
    Abstract:
    Spectroscopic and crystallographic data are presented for salts containing the [V(OH(2))(6)](3+) cation, providing a rigorous test of the ability of the angular overlap model (AOM) to inter-relate the electronic and molecular structure of integer-spin complexes. High-field multifrequency EPR provides a very precise definition of the ground-state spin-Hamiltonian parameters, while single-crystal absorption measurements enable the energies of excited ligand-field states to be identified. The EPR study of vanadium(III) as an impurity in guanidinium gallium sulfate is particularly instructive, with fine-structure observed attributable to crystallographically distinct [V(OH(2))(6)](3+) cations, hyperfine coupling, and ferroelectric domains. The electronic structure of the complex depends strongly on the mode of coordination of the water molecules to the vanadium(III) cation, as revealed by single-crystal neutron and X-ray diffraction measurements, and is also sensitive to the isotopic abundance. It is shown that the AOM gives a very good account of the change in the electronic structure, as a function of geometric coordinates of the [V(OH(2))(6)](3+) cation. However, the ligand-field analysis is inconsistent with the profiles of electronic transitions between ligand-field terms.
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