基于金属氧簇和铜-四氮唑配合物构建的空旷骨架:合成、结构及性能  

A Series of Open-Frameworks Constructed From Polyoxoanion Clusters and Copper-tetrazolate Complexes:Synthesis,Structure and Properties

作　　者：李新雄[1] 程琳[1] 方伟慧[1] 杨国昱[1] 

机构地区：[1]中国科学院福建物质结构研究所结构化学国家重点实验室,福州350002

出　　处：《化学学报》2013年第2期179-185,共7页Acta Chimica Sinica

基　　金：国家自然科学基金(Nos.91122028;21221001);973计划(No.2011CB932504)资助~~

摘　　要：在水热条件下,通过CuCl2 6H2O、5-(2-吡啶基)-四唑与不同的金属氧簇阴离子反应,合成了3个基于金属氧簇与铜-四氮唑构建的空旷骨架:Cu4(2-ptz)4(H2O)7SiW12O40 4H2O(1),Cu5(2-ptz)6(OH)(H2O)3PW12O40 H2O(2),Cu9(μ-O)6(2-ptz)6(H2O)9(H6P2W18O62)3H2O(3)(2-ptz=5-(2-吡啶基)-四唑),并通过元素分析、红外光谱、热失重曲线、紫外-可见光谱、粉末衍射和单晶X射线衍射等手段进行了表征.结构分析表明:它们均为三维结构.化合物1是由分立的Z字形的Cu-(2-ptz)配合物单元与412 40SiW O-簇阴离子连接而成;化合物2是由二维的Cu-(2-ptz)网络与312 40PW O-簇单元桥连形成的;化合物3则是一个不常见的基于一维Cu-(2-ptz)链与62 18 62P W O-簇单元构建的.磁性研究结果表明:化合物1和2表现出反铁磁性,而化合物3表现出不常见的亚铁磁性.Polyoxometalates（POMs） are discrete metal-oxygen clusters with different shapes,sizes,and compositions,which provides a variety of structural building units（SBUs） for making novel and robust POM-based cluster-organic frameworks.Therefore,the combination of POM clusters and metal-organic frameworks will open up a new avenue for the creation of a variety of novel functional materials.Recent years,the hydrothermal technique proved to be a particularly powerful synthetic means of making crystals of numerous organic-inorganic hybrids.In this paper,three organic-inorganic hybrid openframeworks constructed from different types of polyoxoanion cluster units and Cu-（2-ptz）（2-ptz=5-（2-pyridyl）-tetrazole） complexes,Cu4（2-ptz）4（H2O）7SiW12O40 4H2O（1）,Cu5（2-ptz）6（OH）（H2O）3PW12O40 H2O（2）,Cu9（μ-O）6（2-ptz）6（H2O）9（H6P2W18O62） 3H2O（3） have been hydrothermally made and structurally characterized by elemental analyses,infrared spectrum（IR） spectroscopy,thermogravimetric（TG） analyses,ultraviolet-visable diffuse reflectance spectrum（UV-DSR）,powder X-ray diffractions（PXRD）,and single-crystal X-ray structural analyses,respectively.Structure analyses reveal that compounds 1～3 are three-dimensional（3-D） frameworks.The structure of 1 is built up of the isolated zigzag Cu-（2-ptz） complex segments and 4 12 40 SiW O-clusters;2 is constructed from the 2-D Cu-（2-ptz） networks and 3 12 40 PW O-cluster pillars;while 3 is made of the linear Cu-（2-ptz） chains and 6 2 18 62 P W O-clusters.Magnetic measurements indicated that compounds 1 and 2 exhibit antiferromagnetic interactions between Cu ions,while compound 3 display ferrimagnetic coupling behavior.UV-DSR spectra indicate that compounds 1～3 are potential semiconductor materials.The successfully syntheses of compounds 1～3 not only testify that the shapes and the number of negative charges of POM anions have an important influence on the self-assembly of organic-inorganic hybrid POM-based mate

关 键 词：金属氧簇 空旷骨架 有机-无机杂化材料 水热合成 磁性能 

分 类 号：O641.4[理学—物理化学]