Organic鈥揑norganic Hybrid Materials Based on Basket-like {Ca鈯侾6Mo18O73} Cages

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• 作者：He Zhang ; Kai Yu ; Jing-hua Lv ; Li-hong Gong ; Chun-mei Wang ; Chun-xiao Wang ; Di Sun ; Bai-Bin Zhou
• 刊名：Inorganic Chemistry
• 出版年：2015
• 出版时间：July 20, 2015
• 年：2015
• 卷：54
• 期：14
• 页码：6744-6757
• 全文大小：1337K
• ISSN：1520-510X

文摘

Four basket-like organic鈥搃norganic hybrids, formulated as [{Cu^II(H₂O)₂}{Ca₄(H₂O)₄(HO_0.5)₃(en)₂}{Ca鈯侾₆Mo₄^VMo₁₄^VIO₇₃}]路7H₂O (1), (H₄bth)[{Fe^II(H₂O)}{Ca鈯侾₆Mo₁₈^VIO₇₃}]路4H₂O (2), (H₂bih)₃[{Cu^II(H₂O)₂}{Ca鈯侾₆Mo₂^VMo₁₆^VIO₇₃}]路2H₂O (3), (H₂bib)₃[{Fe^II(H₂O)₂}{Ca鈯侾₆Mo₂^V Mo₁₆^VIO₇₃}]路4H₂O (4), (bth = 1,6-bis(triazole)hexane; bih = 1,6-bis(imidazol)hexane; bib = 1,4-bis(imidazole)butane) have been hydrothermally synthesized and fully characterized. Compounds 1鈥?b>4 contain polyoxoanion [Ca鈯侾₆Mo_n^VMo_18鈥?i>n^VIO₇₃]^{(6+n)鈥?/sup> (n = 0, 2, or 4) (abbreviated as {P₆Mo₁₈O₇₃}) as a basic building block, which is composed of a 鈥渂asket body鈥?{P₂Mo₁₄} unit and a 鈥渉andle鈥?liked {P₄Mo₄} fragment encasing an alkaline-earth metal Ca2+ cation in the cage. Compound 1 exhibits an infrequent 2D layer structure linked by the Cu(H₂O)₂ linker and an uncommon tetranuclear calcium complex, while compound 2 is 8-connected 2-D layers connected by binuclear {Fe₂(H₂O)₃} segaments, which are observed for the first time as 2-D basket-like assemblies. Compounds 3 and 4 are similar 1D Z-typed chains bonded by M(H₂O)₂ units (M = Cu for 3 and Fe for 4). The optical band gaps of 1鈥?b>4 reveal their semiconductive natures. They exhibit universal highly efficient degradation ability for typical dyes such as methylene blue, methyl orange, and rhodamine B under UV light. The lifetime and catalysis mechanism of the catalysts have been investigated. The compounds also show good bifunctional electrocatalytic behavior for oxidation of amino acids and reduction of NO₂鈥?/sup>.}