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

doi:10.6023/A12090706

化学学报 ›› 2013, Vol. 71 ›› Issue (02): 179-185.DOI: 10.6023/A12090706 上一篇下一篇

研究论文

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

李新雄, 程琳, 方伟慧, 杨国昱

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

投稿日期:2012-09-24 发布日期:2013-01-11
通讯作者: 杨国昱 E-mail:ygy@fjirsm.ac.cn
基金资助:
项目受国家自然科学基金(Nos. 91122028, 21221001)及973计划(No. 2011CB932504)资助.

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

Li Xinxiong, Cheng Lin, Fang Weihui, Yang Guoyu

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

Received:2012-09-24 Published:2013-01-11
Supported by:
Project supported by the National Natural Science Foundation of China (Nos. 91122028, 21221001) and the 973 Program (No. 2011CB932504).

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1. 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.PDF(423KB)

摘要/Abstract

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SiW₁₂O₄₀^4-簇阴离子连接而成; 化合物2是由二维的Cu-(2-ptz)网络与PW₁₂O₄₀^3-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PW₁₈O₆₂^6-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.

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

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 open- frameworks 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 SiW₁₂O₄₀^4- clusters; 2 is constructed from the 2-D Cu-(2-ptz) networks and PW₁₂O₄₀^3- cluster pillars; while 3 is made of the linear Cu-(2-ptz) chains and PW₁₈O₆₂^6- 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 materials, but also may open up possibilities for the design and construction of new POM-based frameworks with particular functions in the near future.

Key words: polyoxometalate, organic-inorganic hybrid, hydrothermal synthesis, copper, property

引用此文

李新雄, 程琳, 方伟慧, 杨国昱. 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[J]. 化学学报, 2013, 71(02): 179-185.

Li Xinxiong, Cheng Lin, Fang Weihui, Yang Guoyu. A Series of Open-Frameworks Constructed From Polyoxoanion Clusters and Copper-tetrazolate Complexes: Synthesis, Structure and Properties[J]. Acta Chimica Sinica, 2013, 71(02): 179-185.

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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

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

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