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

Kittilstved, Kevin Richard; Sorgho, Lilit Aboshyan; Amstutz, Nahid; Tregenna-Piggott, Philip L.W.; Hauser, Andreas

doi:10.1021/ic900613p

Scientific article

English

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

Contributors

Kittilstved, Kevin Richard; Sorgho, Lilit Aboshyan; Amstutz, Nahid; Tregenna-Piggott, Philip L.W.; Hauser, Andreas

Published in

Inorganic chemistry, vol. 48, no. 16, p. 7750-7764

Publication date

2009

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 spectroscopy
Zero-field splittings
Anisotropic ligand fields
Hydrogen bonding

UNIGE affiliation entities

Faculté des sciences / Section de chimie et biochimie / Département de chimie physique

UNIGE research groups

Groupe Hauser

Citation (ISO format)

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. doi: 10.1021/ic900613p

Article (Published version)

Identifiers

PID : unige:3542
DOI : 10.1021/ic900613p

Journal ISSN

0020-1669

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Creation

02/10/2009 15:17:56

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02/10/2009 15:17:56

Update

14/03/2023 15:15:14

Status update

14/03/2023 15:15:14

Last indexation

10/06/2025 21:29:36

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

Contributors

Published in

Publication date

Abstract

Keywords

UNIGE affiliation entities

UNIGE research groups

Citation (ISO format)

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Journal ISSN

Technical informations

Creation

First validation

Update

Status update

Last indexation