Abstract
The molecular structure and magnetic properties of alkoxy-polyoxovanadates [VIV n VV 6−n O7(OR)12]4−n (n = 4, 3, 2) were studied within the framework of the DFT approach. The equilibrium geometric configurations of all complexes studied in this work are characterized by a distorted octahedral hexavanadate core; the unpaired d-electrons are localized on the metal centers (VIV). The localized spin density distribution is also retained in the low-temperature crystal structures of the compounds whose magnetic properties are described by the Heisenberg-Dirac-van Vleck exchange spin Hamiltonian. The exchange parameters calculated using the broken symmetry formalism suggest predominance of ferromagnetic coupling between vanadium(IV) ions in the μ-OR bridged dimeric units {VIVO(OR)VIV} and in the diagonal pairs {VIVOVIV} (n = 4). The results obtained indicate that the magnitude and sign of the exchange parameters in the isostructural dimeric units within the hexavanadate core depend on the total number of unpaired electrons in the system.
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Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2462–2468, December, 2008.
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Zueva, E.M., Petrova, M.M., Borshch, S.A. et al. Exchange coupling in alkoxy-polyoxovanadates [VIV n VV 6−n O7(OR)12]4−n (n = 4, 3, 2). Russ Chem Bull 57, 2513–2519 (2008). https://doi.org/10.1007/s11172-008-0361-8
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DOI: https://doi.org/10.1007/s11172-008-0361-8