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摘要
Polyoxometalates (P0Ms) 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 Emilieworks. 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-pyridy1)-tetrazole) complexes, Cu-4(2-ptz)(4)(H2O)(7)SiW12O40 center dot 4H(2)O (1), Cu-5(2-ptz)(6)(OH)(H2O)(3)PW12O40 center dot H2O (2), Cu-9(mu-O)6(2-ptz)(6)(H2O)(9)(H6P2W18O62)center dot 3H(2)O (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 similar to 3 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 P-2 W18O626- - 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 similar to 3 are potential semiconductor materials. The successfully syntheses of compounds 1 similar to 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.
- 出版日期2013-2-15
- 单位中国科学院福建物质结构研究所
