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Ground-State Electronic Structure of Vanadium(III) Trisoxalate in Hydrated Compounds

Sorgho, Lilit Aboshyan
Amstutz, Nahid
Tregenna-Piggott, Philip L.W.
Published in Inorganic Chemistry. 2009, vol. 48, no. 16, p. 7750-7764
Abstract The ground-state electronic structures of K3V(ox)3·3H2O, Na3V(ox)3·5H2O, and NaMgAl1−xVx(ox)3·9H2O (0 < x ≤ 1, ox = C2O42−) have been studied by Fourier-transform electronic absorption and inelastic neutron scattering spectroscopies. High-resolution absorption spectra of the 3Γ(t2g2) → 1Γ(t2g2) spin-forbidden electronic origins and inelastic neutron scattering measurements of the pseudo-octahedral [V(ox)3]3− complex anion below 30 K exhibit both axial and rhombic components to the zero-field-splittings (ZFSs). Analysis of the ground-state ZFS using the conventional S = 1 spin Hamiltonian reveals that the axial ZFS component changes sign from positive values for K3V(ox)3·3H2O (D ≈ +5.3 cm−1) and Na3V(ox)3·5H2O (D ≈ +7.2 cm−1) to negative values for NaMgAl1−xVx(ox)3·9H2O (D ≈ −9.8 cm−1 for x = 0.013, and D ≈ −12.7 cm−1 for x = 1) with an additional rhombic component, |E|, that varies between 0.8 and 2 cm−1. On the basis of existing crystallographic data, this phenomenon can be identified as due to variations in the axial and rhombic ligand fields resulting from outer-sphere H-bonding between crystalline water molecules and the oxalate ligands. Spectroscopic evidence of a crystallographic phase change is also observed for K3V(ox)3·3Y2O (Y = H or D) with three distinct lattice sites below 30 K, each with a unique ground-state electronic structure.
Keywords High-resolution spectroscopyZero-field splittingsAnisotropic ligand fieldsHydrogen bonding
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Research group Groupe Hauser
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KITTILSTVED, Kevin Richard et al. Ground-State Electronic Structure of Vanadium(III) Trisoxalate in Hydrated Compounds. In: Inorganic Chemistry, 2009, vol. 48, n° 16, p. 7750-7764. https://archive-ouverte.unige.ch/unige:3542

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Deposited on : 2009-10-02

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