水热条件下缺位多金属氧酸盐与高核过渡金属簇的组合。3. [Cu(enMe)2]2{[Cu(enMe)2(H2O)]2[Cu6(enMe)2(B-a-SiW9O34)2]}.4H2O的结构与表征

Combination of lacunary polyoxometalates and high-nuclear transition metal clusters under hydrothermal conditions. 3. Structure and characterization of [Cu(enMe)2]2{[Cu(enMe)2(H2O)]2[Cu6(enMe)2(B-a-SiW9O34)2]}.4H2O.

作者信息

Zheng Shou-Tian, Yuan Da-Qiang, Zhang Jie, Yang Guo-Yu

机构信息

State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002, China.

出版信息

Inorg Chem. 2007 May 28;46(11):4569-74. doi: 10.1021/ic070160c. Epub 2007 Apr 26.

DOI:10.1021/ic070160c

PMID:17458958

Abstract

A novel sandwich-type polyoxometalate incorporating a unique hybrid hexanuclear copper cluster, [Cu(enMe)2]2{[Cu(enMe)2(H2O)]2[Cu6(enMe)2(B-a-SiW9O34)2]}.4H2O (1, enMe=1,2-diaminopropane), has been hydrothermally synthesized and structurally characterized by the elemental analyses, IR spectroscopy, TG analysis, magnetic properties, and single-crystal X-ray diffraction analysis. Crystal data for 1: triclinic, P; a=12.5105(2), b=14.3710(2), c=17.2687(2) A; alpha=98.834(1), beta=110.744(1), gamma=104.711(1) degrees; V=2704.57(7) A3; rho=3.646 g/cm3; Z=1. X-ray crystallographic study shows that the molecular structure of 1 contains 10 copper ions: Six of them form an unprecedented inorganic-organic hybrid Cu6 cluster via edge-sharing combination of two CuO6 octahedra, two CuO5, and two CuO3N2 square pyramids and are encapsulated between two {B-a-SiW9O34} units. Two of them form two [Cu(enMe)2(H2O)]2+ complexes and further attach to the two {B-a-SiW9O34} units via two Cu-O=W bridges, acting as a decorated role. The remaining two form isolated [Cu(enMe)2]2+ complexes playing roles of charge-compensation and space-fillers. Magnetization measurement reveals that the hexanuclear copper cluster exhibits overall ferromagnetic interactions.

摘要

一种新型夹心型多金属氧酸盐，[Cu(enMe)2]2{[Cu(enMe)2(H2O)]2[Cu6(enMe)2(B-a-SiW9O34)2]}.4H2O (1, enMe = 1,2-二氨基丙烷)，已通过水热法合成，并通过元素分析、红外光谱、热重分析、磁性和单晶X射线衍射分析对其结构进行了表征。1的晶体数据：三斜晶系，P；a = 12.5105(2)，b = 14.3710(2)，c = 17.2687(2) Å；α = 98.834(1)，β = 110.744(1)，γ = 104.711(1)°；V = 2704.57(7) Å3；ρ = 3.646 g/cm3；Z = 1。X射线晶体学研究表明，1的分子结构包含10个铜离子：其中6个通过两个CuO6八面体、两个CuO5和两个CuO3N2方形金字塔的边共享组合形成一个前所未有的无机-有机杂化Cu6簇，并被封装在两个{B-a-SiW9O34}单元之间。其中两个形成两个[Cu(enMe)2(H2O)]2+配合物，并通过两个Cu-O=W桥进一步连接到两个{B-a-SiW9O34}单元上，起到修饰作用。其余两个形成孤立的[Cu(enMe)2]2+配合物，起到电荷补偿和空间填充的作用。磁化测量表明，六核铜簇表现出整体铁磁相互作用。