基于咪唑衍生物和2,5⁃二甲氧基对苯二甲酸的Zn(Ⅱ)⁃MOFs的合成、晶体结构和荧光性质

Three Zn(Ⅱ)⁃MOFs Based on Imidazole Derivatives and 2,5⁃Dimethoxyterephthalic Acid:Syntheses,Crystal Structures,and Fluorescence Properties

在2,5-二甲氧基对苯二甲酸(H_(2)DTA)的存在下,不同结构的咪唑衍生物1,2,4,5-四(1H-咪唑-1-基)苯(1,2,4,5-TIB)、1,4-双(4-甲基-1H-咪唑-1-基)苯(1,4-BMIB)和1,4-双(4-甲基-1H-咪唑-1-基)萘(1,4-BMIN)在溶剂热条件下分别与锌离子反应构筑出3个三维金属有机骨架:{[Zn(DTA)(1,2,4,5-TIB)_(0.5)]·1.5H_(2)O}_(n)(1)、[Zn(DTA)(1,4-BMIB)_(0.5)(H_(2)O)]_(n)(2)和{[Zn(DTA)(1,4-BMIN)]·H_(2)O}_(n)(3)。单晶结构解析揭示3个配合物均属于单斜晶系。其中,四配位1,2,4,5-TIB参与构筑的配合物1具有拓扑符号为(6^(2).8^(4))的四连接框架。而具有纤细骨架和低配位数的1,4-BMIB与1,4-BMIN参与构建的配合物2和3则分别是二重穿插的pcu型和三重穿插的dia型框架。此外,对比配体和配合物的荧光发射光谱,发现配合物的荧光较配体有了明显的增强和蓝移现象。

In the presence of 2,5-dimethoxyterephthalic acid(H_(2)DTA),three 3D metal-organic frameworks,namely{[Zn(DTA)(1,2,4,5-TIB)_(0.5)]·1.5H_(2)O}_(n)(1),[Zn(DTA)(1,4-BMIB)_(0.5)(H_(2)O)]_(n)(2),and{[Zn(DTA)(1,4-BMIN)]·H_(2)O}_(n)(3),have been synthesized by using imidazole derivatives 1,2,4,5-tetra(1H-imidazol-1-yl)benzene(1,2,4,5-TIB),1,4-bis(4-methyl-1H-imidazol-1-yl)benzene(1,4-BMIB),and 1,4-bis(4-methyl-1H-imidazol-1-yl)naphthalene(1,4-BMIN)as ligands to react to zinc ions,respectively.Their structures and fluorescent properties were studied.Single crystal X-ray diffraction analysis reveals that all complexes belong to the monoclinic crystal system.Among them,complex 1 based on four-coordinated 1,2,4,5-TIB is a four-connected framework with a point symbol of(62.84).Compared with complex 1,slim 1,4-BMIB and 1,4-BMIN ligands with low coordination numbers caused that complexes 2 and 3 are 2-fold interpenetration pcu-type and 3-fold interpenetration dia-type networks,respectively.Furthermore,the fluorescent properties of complexes 1-3 were also studied,and their emission spectra had a significant enhancement and blue shift compared to the emission peak of the ligands.CCDC:2129603,1;2129604,2;2129604,3.