Decoding the role of encapsulated ions in the electronic and magnetic properties of mixed-valence polyoxovanadate capsules {X@V22O54} (X = ClO4-, SCN-, VO2F2-): a combined theoretical approach

Identifier:  imarina:6021015

Handle: https://hdl.handle.net/20.500.11797/imarina6021015

Authors:  Notario-Estévez, A; Kozlowski, P; Linnenberg, O; de Graaf, C; López, X; Monakhov, KY

Abstract:
The electronic structure and magnetism of mixed-valence, host-guest polyoxovanadates {X@VIV/V22O(54)} with diamagnetic (X =) ClO4- (T-d, 1) and SCN- (C-v, 2) template anions are assessed by means of two theoretical methods: density functional theory and effective Hamiltonian calculations. The results are compared to those obtained for another member of this family with X = VO2F2- (C-2v, 3) (see P. Kozowski et al., Phys. Chem. Chem. Phys., 2017, 19, 29767-29771), for which complementary data are also acquired. It is demonstrated that the X guest anions strongly influence the electronic and magnetic properties of the system, leading to various valence states of vanadium and modifying V-O-V exchange interactions. Our findings are concordant with and elucidate the available experimental data (see K. Y. Monakhov et al., Chem. - Eur. J., 2015, 21, 2387-2397).