三例基于5-(二甲基氨基)间苯二甲酸的锌(Ⅱ)/铜(Ⅱ)配合物的合成、晶体结构、Hirshfeld表面分析和荧光性质  

Synthesis,structure,fluorescence properties,and Hirshfeld surface analysis of three Zn(Ⅱ)/Cu(Ⅱ)complexes based on 5-(dimethylamino)isophthalic acid

作　　者：王凯民 顾雄 邓娜 于红梅 叶艳青 马钰璐 WANG Kaimin;GU Xiong;DENG Na;YU Hongmei;YE Yanqin;MA Yulu(School of Chemistry&Environment,Yunnan Minzu University,Kunming 650504,China;School of Pharmaceutical Sciences and Yunnan Key Laboratory of Pharmacology for Natural Products,Kunming Medical University,Kunming 650500,China;College of Modern Biomedical Industry,Kunming Medical University,Kunming 650500,China)

机构地区：[1]云南民族大学化学与环境学院,昆明650504 [2]昆明医科大学药学院暨天然药物药理重点实验室,昆明650500 [3]昆明医科大学现代生物医药产业学院,昆明650500

出　　处：《无机化学学报》2024年第7期1397-1408,共12页Chinese Journal of Inorganic Chemistry

基　　金：国家自然科学基金(No.21762049);云南省科技厅基础研究项目(No.202301AT070264);云南省教育厅科学研究基金(No.2023J0595);昆明医科大学2022年度本科教学质量与教学改革工程一流课程项目(No.2022JXZ018);云南省本科教育教学改革研究项目(No.JG2023001)资助。

摘　　要：利用配体5-(二甲基氨基)间苯二甲酸(H_(2)dia)和咪唑(mdz)分别与锌(Ⅱ)和铜(Ⅱ)金属盐反应,制备了3例过渡金属配合物[Zn(dia)(mdz)_(2)]·2H_(2)O(1)、[Cu(dia)(mdz)_(2)(DMF)](2)和[Cu(dia)(mdz)_(2)]·H_(2)O(3)。利用单晶X射线衍射、元素分析、红外光谱、热重和Hirshfeld表面分析对其进行了结构表征。结果表明配合物1和2为一维线状链,1中每个四配位的Zn(Ⅱ)处于变形四面体中心,2中Cu(Ⅱ)中心拥有五配位的三角双锥几何构型。改变合成溶剂条件得到锯齿形一维链状配合物3,其四配位Cu(Ⅱ)中心展现出对称平面四边形构型。上述结果说明,金属离子几何构型以及合成溶剂可能对配合物结构具有重要影响。丰富的分子间氢键帮助3例配合物形成稳定的三维超分子结构。热重分析表明,3例配合物均具有良好的热稳定性。固体荧光分析表明配合物1具有较强荧光性,而配合物2和3荧光强度均远低于配体。5-(dimethylamino)isophthalic acid(H_(2)dia)and 1H-imidazole(mdz)were used as ligands to react with Zn(Ⅱ)or Cu(Ⅱ)metal salts to generate three new transition metal complexes[Zn(dia)(mdz)_(2)]·2H_(2)O(1),[Cu(dia)(mdz)_(2)(DMF)](2)and[Cu(dia)(mdz)_(2)]·H_(2)O(3).Their structures were characterized by single-crystal X-ray diffraction,elemental analysis,IR,thermogravimetric analyses,and Hirshfeld surface analyses.The results revealed that complexes 1 and 2 possess 1D linear chains,each four-coordinated Zn(Ⅱ)of 1 is located in the geometric center of the distorted tetrahedron,but the Cu(Ⅱ)metal center of 2 is five-coordinated and holds a triangular bipyramidal geometry.The zigzag 1D chain of complex 3 was obtained by changing the solvent in the synthesis,and the four-coordinated Cu(Ⅱ)ion is in the centre of the square planar.Results indicate that the geometries of metal centers and synthetic solvents have important effects on the structures of complexes.Abundant intermolecular hydrogen bonding plays an important role in the stability of their 3D supramolecular structures.Thermogravimetric analyses revealed that the complexes have good thermal stabilities.Solid fluorescence analyses showed that complex 1 had excellent fluorescence,but the fluorescence intensities of complexes 2 and 3 were much lower than those of ligands.CCDC:2323564,1;2323565,2;2323566,3.

关 键 词：配合物 过渡金属 晶体结构 Hirshfeld表面分析 荧光性质 

分 类 号：O614.121[理学—无机化学] O614.241[理学—化学]