一系列基于[(ZnO6)(As3O3)2Mo6O18]4-和[HxAs2Mo6O26](6-x)-簇作为次级构筑单元的新型有机-无机钼砷酸盐配合物。

A series of new organic-inorganic molybdenum arsenate complexes based on [(ZnO6)(As3O3)2Mo6O18]4- and [HxAs2Mo6O26](6-x)- clusters as SBUs.

作者信息

Sun Chunyan, Li Yangguang, Wang Enbo, Xiao Dongrong, An Haiyan, Xu Lin

机构信息

Key Laboratory of Polyoxometalate Science of Ministry of Education, Institute of Polyoxometalate Chemistry, Department of Chemistry, Northeast Normal University, Changchun, 130024, P. R. China.

出版信息

Inorg Chem. 2007 Mar 5;46(5):1563-74. doi: 10.1021/ic061227j. Epub 2007 Feb 3.

DOI:10.1021/ic061227j

PMID:17274612

Abstract

By synthesizing the novel molybdenum arsenate complexes, we have obtained eight new structures, namely, (4,4'-bipy)[Zn(4,4'-bipy)2(H2O)2]2[(ZnO6)(AsIII3O3)2Mo6O18].7H2O, 1, [Zn(phen)2(H2O)]2[(ZnO6)(AsIII3O3)2Mo6O18].4H2O, 2, [Zn(2,2'-bipy)2(H2O)]2[(ZnO6)(AsIII3O3)2Mo6O18].4H2O, 3, [Zn(H4,4'-bipy)2(H2O)4][(ZnO6)(AsIII3O3)2Mo6O18].8H2O, 4, (H24,4'-bipy)[CuI(4,4'-bipy)]2[H2AsV2Mo6O26].H2O, 5, (H24,4'-bipy)3[AsV2Mo6O26].4H2O, 6, (H24,4'-bipy)3[AsV2Mo6O26(H2O)].4H2O, 7, and (H24,4'-bipy)2.5(H3O)[AsV2Mo6O26(H2O)].1.25H2O, 8 (4,4'-bipy = 4,4'-bipyridine, 2,2'-bipy = 2,2'-bipyridine, phen = 1,10-phenanthroline). These structures were determined by single-crystal X-ray diffraction analysis and were further characterized by elemental analysis, IR, XPS spectroscopy, and TG analysis. The structure of 1 is constructed from two-dimensional square gridlike sheets linked by the polyanions [(ZnO6)(AsIII3O3)2Mo6O18]4- via hydrogen-bonding interactions to form a three-dimensional supramolecular framework with two types of channels. Compounds 2 and 3 display similar bisupported structures. Compound 4 features a three-dimensional supramolecular architecture. Compound 5 possesses a 1D infinite ladderlike ribbon. Compounds 6-8 are discrete structures exhibiting three isomeric forms of HxAs2Mo6O26-. Furthermore, compound 8 represents a new isomer B'-[As2Mo6O26(H2O)]6-. In addition, the fluorescent properties of compounds 1-3 are reported.

摘要

通过合成新型砷酸钼配合物，我们得到了8种新结构，即(4,4'-联吡啶)[Zn(4,4'-联吡啶)2(H2O)2]2[(ZnO6)(AsIII3O3)2Mo6O18].7H2O，1；[Zn(邻菲罗啉)2(H2O)]2[(ZnO6)(AsIII3O3)2Mo6O18].4H2O，2；[Zn(2,2'-联吡啶)2(H2O)]2[(ZnO6)(AsIII3O3)2Mo6O18].4H2O，3；[Zn(H4,4'-联吡啶)2(H2O)4][(ZnO6)(AsIII3O3)2Mo6O18].8H2O，4；(H24,4'-联吡啶)[CuI(4,4'-联吡啶)]2[H2AsV2Mo6O26].H2O，5；(H24,4'-联吡啶)3[AsV2Mo6O26].4H2O，6；(H24,4'-联吡啶)3[AsV2Mo6O26(H2O)].4H2O，7；以及(H24,4'-联吡啶)2.5(H3O)[AsV2Mo6O26(H2O)].1.25H2O，8（4,4'-联吡啶 = 4,4'-联吡啶，2,2'-联吡啶 = 2,2'-联吡啶，邻菲罗啉 = 1,10-菲咯啉）。这些结构通过单晶X射线衍射分析确定，并通过元素分析、红外光谱、X射线光电子能谱和热重分析进一步表征。1的结构由二维方形网格状片层构成，这些片层通过聚阴离子[(ZnO6)(AsIII3O3)2Mo6O18]4-通过氢键相互作用连接在一起形成具有两种类型通道的三维超分子框架。化合物2和3呈现出类似的双支撑结构。化合物4具有三维超分子结构。化合物5具有一维无限阶梯状带。化合物6 - 8是呈现[HxAs2Mo6O26](6 - x)-三种异构体形式的离散结构。此外，化合物8代表一种新的异构体B'-[As2Mo6O26(H2O)]6-。另外，还报道了化合物1 - 3的荧光性质。