含有分离电荷中心的吡啶鎓两性离子型Cd(Ⅱ)配合物的合成、结构和荧光性研究  

Synthesis,crystal structure and fluorescence property of Cd(Ⅱ)complex containing separate charge centers based on pyridinium zwitterionic ligand

作　　者：王凯民 郭津榕 张倩 唐怀军 王玉娜 马钰璐 WANG Kai-min;GUO Jin-rong;ZHANG Qian;TANG Huai-jun;WANG Yu-na;MA Yu-lu(School of Chemistry&Environment,Yunnan Minzu University,Kunming 650504,Yunnan,China;School of Pharmaceutical Sciences,Yunnan Key Laboratory of Pharmacology for Natural Products,Kunming Medical University,Kunming 650500,Yunnan,China)

机构地区：[1]云南民族大学化学与环境学院,云南昆明650504 [2]昆明医科大学药学院暨天然药物药理重点实验室,云南昆明650500

出　　处：《云南大学学报（自然科学版）》2022年第3期576-584,共9页Journal of Yunnan University(Natural Sciences Edition)

基　　金：国家自然科学基金(21762049);云南省科技厅基础研究项目(202001AU070111);云南省教育厅科学研究基金(2020J0140).

摘　　要：以半刚性吡啶鎓两性离子化合物1,1′-((2,3,5,6-四甲基-1,4-亚苯基)双(亚甲基))双(4-羧基吡啶-1-鎓)氯化物(H_(2)LCl_(2))为配体,采用常温挥发法得到了去质子化配体(L)的单晶,并用配体H_(2)LCl_(2)与CdCl_(2)在中性pH常温条件下合成了一例具有分离正负电荷中心配合物[CdCl_(2)(H_(2)O)_(2)]·H_(2)O.单晶X射线衍射结果表明,去质子化配体L结晶于Monoclinic晶系的I2/m空间群,其结构中具有分离的正负电荷中心.配合物结晶于Monoclinic晶系P21/n空间群,相邻Cd(Ⅱ)离子间通过相同朝向的“凹”字形去质子化配体桥连形成梯形一维链,而后一维链间通过丰富的氢键作用形成三维超分子结构,其骨架延续了配体的特点,存在分离的电荷.此外,荧光研究表明,配合物显示了与配体相似的蓝色荧光特征,但由于配合物体系形成后共轭程度的增强,电子转移跃迁的存在,配合物的荧光强度较配体增强,发射峰位置出现蓝移,最强发射峰在436 nm处.The flexible zwitterion compound 1,1'-((2,3,5,6-tetramethyl-1,4-phenylene)bis(methylene))bis(4-carboxypyridin-1-ium)chloride was used as the ligand to obtain the single crystal of deprotonated ligand(L)by the room temperature volatilization method.Then,a novel coordination compound with separated positive and negative charge centers[CdLCl_(2)(H_(2)O)_(2)]·H_(2)O was synthesized with the H_(2)LCl_(2) ligand and CdCl_(2) under neutral pH conditions at room temperature.Single-crystal X-ray diffraction results show that the deprotonated ligand L crystallizes in the monoclinic space group I2/m,and its structure has separated charge centers.In addition,the complex crystallizes in the P21/n space group of monoclinic crystal system.The adjacent Cd(Ⅱ)ions are bridged by the concave-shaped ligands L in the same orientation to form a 1D chains.Then these chains are further linked by hydrogen bonds to get three-dimensional supramolecular architecture.The skeleton carries on the characteristics of the ligand.Fluorescence studies show that the complex shows blue fluorescence characteristics similar to that of ligand.However,due to the enhanced conjugation degree and electron transitions,the fluorescence intensity of the complex is stronger than those of ligands,and there is a blue shift of its emission peak,which is at 436 nm.

关 键 词：吡啶鎓两性离子配体 镉配合物 晶体结构 荧光性质 

分 类 号：O641.4[理学—物理化学] O611.4[理学—化学]