pH and Ligand Dependent Assembly of Well鈥揇awson Arsenomolybdate Capped Architectures

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• 作者：He Zhang ; Kai Yu ; Chunmei Wang ; Zhanhua Su ; Chunxiao Wang ; Di Sun ; Honghong Cai ; Zhaoyi Chen ; Baibin Zhou
• 刊名：Inorganic Chemistry
• 出版年：2014
• 出版时间：December 1, 2014
• 年：2014
• 卷：53
• 期：23
• 页码：12337-12347
• 全文大小：662K
• ISSN：1520-510X

文摘

Five Well鈥揇awson-type arsenomolybdates, formulated as [Cu(2,2鈥?bpy)₂][{Cu(2,2鈥?bpy)}₃{As₂^VMo₂^VMo₁₆^VIO₆₂}]路4H₂O (1), [H₂(4,4鈥?bpy)]_2.5[As^III(As₂^VMo₂^VMo₁₆^VIO₆₂)]路5H₂O (2), (pyr)(imi)(Himi)₃[As₂^III(As₂^VMo₃^VMo₁₅^VIO₆₂)]路3H₂O (3), [As₃^III(As₂^VMo₃^VMo₁₅^VIO₆₂)]路4H₂O (4), and (H₂btp)₃[As₂^VMo₁₈^VIO₆₂]路6H₂O (5) (bpy = bipyridine, pyr = pyrazine, imi = imidazole, btp = 1,5-bis(triazol)pentane), have been hydrothermally synthesized and structurally characterized by the elemental analysis, TG, IR, UV鈥搗is鈥揘IR, XPS, XRD, and single-crystal X-ray diffraction. The structural analysis indicates that compounds 1鈥?b>4 contain rare reduced Dawson {As₂Mo₁₈O₆₂} (abbreviated as {As₂Mo₁₈}) anions as parent cluster unit, which are capped by a certain number of Cu(II) or As(III) species on different coordination positions via altering pH values and organic ligand of the reaction system. Compounds 1 and 2 are asymmetric tricopper and monoarsenate(III) capped assemble by three {Cu(bpy)}²⁺ and a {AsO₃} fragments, respectively. Compounds 3 and 4 are symmetric biarsenate(III) and triarsenate(III) capped cluster by four and six half occupancy {AsO₃} units, respectively. Compound 5 is uncapped {As₂Mo₁₈} structures. Compounds 1鈥?b>4 represent infrequent Dawson arsenomolybdate capped architectures, especially 2鈥?b>4, as arsenate(III) capped Dawson-type assemblies are observed for the first time. Compounds 1鈥?b>5 display good electrocatalytic activity on reduction of nitrite. Compounds 1, 2, 3, and 5 exhibit fluorescent properties in the solid state at room temperature. In addition, magnetic properties of 1鈥?b>4 have been investigated in detail.