3,5-二烷基-1,2,4-三唑衍生物构筑的两个Cu4I4簇配合物的合成、结构和荧光性质

摘要

以3,5-二甲(丙)基-4-氨基-1,2,4-三唑为配体,与CuI在H2O/MeCN混合溶剂热合成了2个构型不同的CuI4超分子化合物{[Cu2(aadmtrz)I2]· CH3CN}n(1)和[Cu2(dptrz)I]n(2)(aadmtrz=4-((1-氨乙基)-氨基)-3,5-二甲基-1,2,4-三唑,dptrz=3,5-二丙基-1,2,4-三唑),并进行了元素分析,红外,X射线粉末衍射及单晶衍射等表征.2个配合物中Cu4I4构型不同,配合物1中,Cu4I4簇连结成一个8环椅式-椅式结构,通过配体连接成(4,4)二维菱形格子结构;而配合物2中,Cu4I4簇呈畸变的立方烷结构,构成了含有19.5％孔隙率三维孔洞聚合物,其结构可简化为(3,4)-连接的拓朴结构.同时,在常温下研究了2个配合物的固体荧光性质.%Two Cu4I4 coordination polymers, {[Cu2(aadmtrz)I2] ·CH3CN}n (1) and [Cu2(dptrz)I]n (2) (aadmtrz=4-((1-aminoethylidene)-amino)-3,5-dimethyl-1,2,4-triazole, dptrz=3,5-dipropyl-1,2,4-triazole), have been synthesized by the solvothermal reactions of CuI and 3,5-dialkyl-4-amino-1,2,4-triazole ligands in mixed H2O/MeCN solution and characterized using elemental analysis, IR, PXRD and single-crystal X-ray diffraction.The structures of the Cu4I4 units in the polymers are different.The Cu4I4 cluster in complex 1 is an inorganic 8-membered ring with a chairchair conformation, while the one in complex 2 is a distorted cube.Complex 1 exhibits 2D 4,4-connected rhombic-grid.Complex 2 is a (3,4)-connected framework with 19.5％ porosity.In addition, the luminescent properties of the complexes in the solid state were also investigated.