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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
  • 期刊名称:Acta Chimica Sinaca
  • 时间:2013.1.1
  • 页码:179-185
  • 分类:O641.4[理学—物理化学;理学—化学]
  • 作者机构:[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
  • 相关基金:国家自然科学基金(Nos.91122028,21221001);973计划(No.2011CB932504)资助
  • 相关项目:无机-有机杂化功能材料
中文摘要:

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.

英文摘要:

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

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