含羧基双席夫碱及其铜(Ⅱ)配合物的合成、晶体结构及其性质
Syntheses, Crystal Structures and Properties of Bis-Schiff Bases Containing Carboxyl and Their Copper(Ⅱ) Complexes
作者单位E-mail
梁楚欣 桂林理工大学化学与生物工程学院, 电磁化学功能物质广西区重点实验室, 桂林 541004  
刘峥 桂林理工大学化学与生物工程学院, 电磁化学功能物质广西区重点实验室, 桂林 541004 lisa4.6@163.com 
梁秋群 桂林理工大学化学与生物工程学院, 电磁化学功能物质广西区重点实验室, 桂林 541004  
唐群 桂林理工大学化学与生物工程学院, 电磁化学功能物质广西区重点实验室, 桂林 541004 tangq@glut.edu.cn 
李海莹 桂林理工大学化学与生物工程学院, 电磁化学功能物质广西区重点实验室, 桂林 541004  
黄何香 桂林理工大学化学与生物工程学院, 电磁化学功能物质广西区重点实验室, 桂林 541004  
张淑芬 桂林理工大学化学与生物工程学院, 电磁化学功能物质广西区重点实验室, 桂林 541004
大连理工大学精细化工重点实验室, 大连 116024 
 
摘要: 利用邻羧基苯甲醛分别与1,3-丙二胺和乙二胺进行缩合得到邻羧基苯甲醛缩1,3-丙二胺双席夫碱(L1)和邻羧基苯甲醛缩乙二胺双席夫碱(L2)。以L1和L2为配体,分别与一水合乙酸铜在无水甲醇中通过溶剂热反应得到2个铜(Ⅱ)配合物[Cu(L1)(CH3OH)](1)和[Cu2(L)2]·2H2O·CH3OH(2),其中邻苯二甲酸单甲酯缩乙二胺双席夫碱(L)为配体L2与甲醇发生加成反应形成的新配体。通过X射线单晶衍射法、红外光谱、元素分析、紫外光谱、荧光光谱、热重分析等测试手段对其进行结构表征与性质研究。单晶结构分析表明:L2为邻羧基苯甲醛缩乙二胺双席夫碱配体,属单斜晶系,I2/a空间群。配合物1属正交晶系,Pbca空间群,Cu(Ⅱ)与一个双席夫碱L1配体和一个甲醇分子配位,形成五配位的四方锥[CuO3N2]构型。配合物2属三斜晶系,P1空间群,Cu(Ⅱ)与配体L的2个氮原子和3个氧原子配位,形成五配位的扭曲三角双锥[CuO3N2]构型,并通过羧基氧原子桥连形成双核铜结构。
关键词: 双席夫碱  铜配合物  晶体结构  荧光性质  热稳定性
基金项目: 广西自然科学基金(No.2016GXNSFAA380109)、国家自然科学基金(No.21501033)和'广西特聘专家'专项经费(No.2401007012)资助项目
Abstract: Based on o-carboxybenzaldehyde-1,3-diaminopropane bis-Schiff base (L1) and o-carboxybenzaldehyde-ethylenediamine bis-Schiff base (L2), two copper(Ⅱ) complexes, namely[Cu(L1)(CH3OH)] (1) and[Cu2(L)2]·2H2O·CH3OH (2), have been prepared by solvothermal synthesis method, where methyl phthalate ethylenediamine bis-Schiff base (L) was formed by the addition reaction of ligand L2 with methanol. The crystal structure of ligand L2 and complex 1,2 was characterized by X-ray single crystal diffraction. The structural analysis indicates that L2 is o-carboxybenzaldehyde ethylenediamine bis-Schiff base ligand, which belongs to monoclinic system, I2/a space group. Complex 1 belongs to the orthorhombic system, Pbca space group, and Cu(Ⅱ) is coordinated with the bis-Schiff base ligand L1 and a methanol molecule to form a penta-coordinated tetragonal[CuO3N2] configuration. Complex 2 belongs to the triclinic system, P1 space group, and Cu(Ⅱ) is coordinated with two nitrogen atoms and three oxygen atoms of the ligand L to form a penta-coordinated twisted triangular bipyramid[CuO3N2] configuration, and the di-nuclear copper structure is formed by bridging a carboxyl oxygen atom. Complexes 1,2 both have a 3D structure construed by highly stable hydrogen bonds. The structure characterization and properties of ligands L1, L2 and complexes 1,2 were studied by IR, elemental analyses, UV, fluorescence and thermogravimetry. The results indicate that bis-Schiff base L1, L2 and complexes 1, 2 have good fluorescence properties and thermal stability. Moreover, complexes 1 and 2 showed strong fluorescence emission at 327 and 323 nm, respectively.
Keywords: Schiff base  copper complex  crystal structure  fluorescence property  thermal stability
投稿时间:2018-10-08 修订日期:2019-04-24
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梁楚欣,刘峥,梁秋群,唐群,李海莹,黄何香,张淑芬.含羧基双席夫碱及其铜(Ⅱ)配合物的合成、晶体结构及其性质[J].无机化学学报,2019,35(7):1130-1138.
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