Synthesis and Structural Characterization of Trimanganese-Containing Polyoxovanadates with Carboxylate Ligands

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• 作者：Tatsuya Maruyama ; Yuji Kikukawa ; Keisuke Kawamoto and Yoshihito Hayashi
• 刊名：European Journal of Inorganic Chemistry
• 出版年：2017
• 出版时间：January 18, 2017
• 年：2017
• 卷：2017
• 期：3
• 页码：596-599
• 全文大小：865K
• ISSN：1099-0682c

文摘

A trimanganese core containing polyoxovanadate {Et₄N}₅[Mn₃(OAc)(H₂O)V₁₀O₃₀] (I; OAc = acetate) was synthesized by the reaction of {Et₄N}[VO₃] with Mn(OAc)₂ (0.3 equiv.) in acetonitrile. The trimanganese core possesses a bridging acetate ligand. To demonstrate the ligand-exchange properties of I, its reaction with benzoic acid (1 equiv.) was conducted and {Et₄N}₅[Mn₃(OBz)(H₂O)V₁₀O₃₀] (II; OBz = benzoate) was formed quantitatively. By using a dicarboxylate, the inorganic–organic–inorganic hybrid {Et₄N}₁₀[{Mn₃(H₂O)V₁₀O₃₀}₂{OOC(CH₂)_nCOO}] [n = 3 (III) and n = 4 (IV)] compounds were synthesized. To compensate the negative–negative repulsion between the anionic groups with a 5– charge, tetraethylammonium cations are sandwiched between the anionic groups in the crystallographic packing. Despite the differences in the bridging carbon numbers, both complexes have the same orientation in the crystal state except for the conformation of the alkyl chains, which suggests the presence of a unique interaction with an anion–cation–anion motif to form V-shaped dimer configurations.