Synthesis, structure, electrochemistry and magnetism of cobalt-, nickel- and zinc-containing [M4(OH)3(H2O)2(-SiW10< /sub>O36.5)2]13- (M = Co2+, Ni2+, and Zn2+)
DALTON TRANSACTIONS(2021)
摘要
Interaction of the trilacunary 9-tungstosilicate [A-alpha-SiW9O34](10-) with cobalt(ii), nickel(ii) and zinc(ii) ions in pH 9 aqueous medium at room temperature led to the formation of the respective M-4-containing heteropolytungstates [M-4(OH)(3)(H2O)(2)(alpha-SiW10O36.5)(2)](13-) (M = Co2+ (1), Ni2+ (2), and Zn2+ (3)). Polyanions 1-3 were characterized in the solid state by single-crystal XRD, FT-IR spectroscopy, and thermogravimetric and elemental analyses. Electrochemical studies showed that the Co2+ ions in 1 can be oxidized to Co3+ and the CVs of the W-VI centers of the polyanions feature well-defined and chemically reversible reduction waves. Magnetic measurements on 1 and 2 showed paramagnetism with complex ferromagnetic and antiferromagnetic interactions. A model was presented for extracting the exchange constants for the magnetic exchange interaction.
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关键词
electrochemistry,zn<sup>2+</sup>,zinc-containing
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