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Mixing Sbᴵᴵᴵ and Geᴵⱽ occupancy in the polyoxovanadate {V₁₄E₈} archetype

Author:
Wendt, Michael, Näther, Christian, van Leusen, Jan, Kögerler, Paul, Bensch, Wolfgang
Source:
Zeitschrift für Naturforschung 2018 v.73 no.11 pp. 773-779
ISSN:
1865-7117
Subject:
anions, antimony, cations, ferrimagnetic materials, magnetic properties, magnetism, mixing, nickel
Abstract:
The first mixed germanato-antimonato derivative of the {V₁₄E₈O₄₂} (E=semi-metal) cluster archetype has been synthesized under hydrothermal conditions and isolated as {Ni(phen)₃}₂[α-Vᴵⱽ₁₄Sbᴵᴵᴵ₅Geᴵⱽ₃O₄₂(OH)₃(H₂O)]· ≈16H₂O (phen=1,10-phenanthroline). In the cluster anion, seven of the eight hetero-metal positions are occupied by disordered Ge/Sb atoms, while one position is fully occupied by Sb atoms. The [V₁₄Sb₅Ge₃O₄₂(OH)₃(H₂O)]⁶⁻ anions are arranged in pairs with remarkably short inter-cluster Sb···O contacts. Bond valence sum calculation strongly suggests that the Sb···O contact must be taken into account as a weak bond. The magnetic properties are dominated by strong intra-cluster antiferromagnetic exchange interactions, and the cluster anion is magnetically quasi-isolated from the spins of the Ni²⁺ complex cations.
Agid:
6198517