Hoffmann, R. A wiki for the life sciences where authorship matters. Nature Genetics (2008)

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Tregenna-Piggott, P.L. et al.

Tregenna-Piggott, Spichiger, Carver, Frey, Meier, Weihe, Cowan, McIntyre, Zahn, Barra,

Structure and bonding of the vanadium(III) hexa-aqua cation. 1. Experimental characterization and ligand-field analysis.

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.[1]

References

Structure and bonding of the vanadium(III) hexa-aqua cation. 1. Experimental characterization and ligand-field analysis. Tregenna-Piggott, P.L., Spichiger, D., Carver, G., Frey, B., Meier, R., Weihe, H., Cowan, J.A., McIntyre, G.J., Zahn, G., Barra, A.L. Inorganic chemistry. (2004) [Pubmed]

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