Acta Chimica Sinica ›› 2013, Vol. 71 ›› Issue (02): 179-185.DOI: 10.6023/A12090706 Previous Articles     Next Articles



李新雄, 程琳, 方伟慧, 杨国昱   

  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
  • 投稿日期:2012-09-24 发布日期:2013-01-11
  • 通讯作者: 杨国昱
  • 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   

  1. 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).

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 13 are three-dimensional (3-D) frameworks. The structure of 1 is built up of the isolated zigzag Cu-(2-ptz) complex segments and SiW12O404- clusters; 2 is constructed from the 2-D Cu-(2-ptz) networks and PW12O403- cluster pillars; while 3 is made of the linear Cu-(2-ptz) chains and PW18O626- 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 13 are potential semiconductor materials. The successfully syntheses of compounds 13 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