基于金属氧簇和稀土镨-含氮配合物构建的三维孔洞骨架化合物的合成、结构和性能研究

Praseodymium-Organic Cation Frameworks with Zeolite Gismondine Topology and Large Cavities from Intersected Channels Templated by Polyoxometalate Counterions

在水热条件下通过稀土金属Pr盐和成簇元素Mo以及含氮有机配体,首次合成了一个三维孔洞型骨架金属有机配位聚合物,并通过元素分析、红外光谱、紫外-可见光谱、粉末衍射和X射线单晶衍射等手段进行了表征和测试.结构分析表明:此化合物为新颖的以Keggin簇阴离子、稀土金属和有机配体构成的有机无机杂化物质.结构特点是沸石型四连接方式形成三维阳离子网络结构{[Pr(H_2O)_4(pdc)]_4}^(4+),且含有大量孔洞,纳米尺寸[Ge Mo_(12)O_(40)]^(4-)作为模板填充在孔洞里,且此化合物具有荧光性质和电化学性质.

A new compound,namely{ [Pr（H2O）4（pdc）]4} [GeMo（12）O（40）]·H2O（1）（ H2pdc = pyridine-2,6-dicarboxylate）,was synthesized and characterized by IR,UV-Vis,powder XRD,elemental analyses and single crystal X-ray diffraction. The compound represented a new example of compound with organic-inorganic hybrid framework constructed from Keggin polyanion,rare earth metal ion and organic ligand. Single crystal X-ray diffraction revealed that the compound consists of a zeolite-like four-connected three-dimensional cationic framework{ [Pr（H2O）4（ pdc）]4}^4＋. Interesting channels exist in the cationic frame work with the gismondine topology,and these channels intersect each other to form large cavities,which are occupied by nano sized[GeMo（12）O（40）]^4- counterion as templates. Moreover,the compound displayed strong photoluminescent and electricatric properties in the solid state at room temperature.