Synthesis and Reversible Transformation of Cu n ‑Bridged (n = 1, 2, or 4) Silicodecatungstate Dimers

Three copper-bridged sandwich-type silicodecatungstate dimers, TBA8[Cu­(γ-SiW10O34)2(CH3CONH)2]·4H2O (Cu-1, TBA = tetra-n-butylammonium), TBA8H4[Cu2(γ-SiW10O36)2H2O]·11H2O·CH3COCH3 (Cu-2), and TBA8H2[Cu4(γ-SiW10O36)2(CH3COO)2]·5H2O (Cu-4) have been selectively synthesized by reactions of divacant la...

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Bibliographic Details
Published in:Inorganic chemistry 2012-11, Vol.51 (21), p.11574-11581
Main Authors: Suzuki, Kosuke, Shinoe, Masahiro, Mizuno, Noritaka
Format: Article
Language:English
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Summary:Three copper-bridged sandwich-type silicodecatungstate dimers, TBA8[Cu­(γ-SiW10O34)2(CH3CONH)2]·4H2O (Cu-1, TBA = tetra-n-butylammonium), TBA8H4[Cu2(γ-SiW10O36)2H2O]·11H2O·CH3COCH3 (Cu-2), and TBA8H2[Cu4(γ-SiW10O36)2(CH3COO)2]·5H2O (Cu-4) have been selectively synthesized by reactions of divacant lacunary TBA4[H4(γ-SiW10O36)] (SiW10) with copper acetate in organic media. The copper cation(s) in Cu-1, Cu-2, and Cu-4 possess square-planar four-coordinate (Cu-1), square-pyramidal five-coordinate (Cu-2), and octahedral six-coordinate (Cu-4) geometries, respectively. These compounds can reversibly be transformed simply by controlling the copper/SiW10 molar ratios in solutions.
ISSN:0020-1669
1520-510X
DOI:10.1021/ic301488a