吡啶鎓类配位聚合物{[Zn(L)Cl_(2)]·4H_(2)O}的合成及结构研究  

Synthesis and Structural Study of Pyridinium Complexes{[Zn(L)Cl_(2)]·4H_(2)O}

作　　者：白旭玲 赵雄 杨冲福 郭津榕 孙蔚青 Bai Xuling;Zhao Xiong;Yang Chongfu;Guo Jinrong;Sun Weiqing(School of Chemistry&Environment,Yunnan Minzu University,Kunming 650504,China)

机构地区：[1]云南民族大学化学与环境学院,云南昆明650504

出　　处：《广东化工》2024年第5期14-16,共3页Guangdong Chemical Industry

基　　金：国家自然科学基金地区基金项目(21961045);云南省教育厅科学研究基金(2020J0326)。

摘　　要：利用半刚性吡啶鎓多羧酸配体1,1’-([1,1’-联苯]-4,4’-二基双(亚甲基))双(4-羧基吡啶-1-鎓)(H2LCl)作为连接体,与Zn^(2+)离子在水热条件下加热至120℃反应72小时成功构筑出一例Zn(Ⅱ)配合物,即{[Zn(L)Cl_(2)]·4H_(2)O}。通过X-单晶衍射对其进行分析,{[Zn(L)Cl_(2)]·4H_(2)O}是一维链状结构,属于单斜晶系,P21/c空间群(晶胞参数a=15.951(6)A,b=9.636(4)A,c=18.849(7)A,α=90°,β=113.240(6)°,γ=90°)。Zn(Ⅱ)中心以四配位的模式连接两个羧基氧原子和两个Cl-离子形成一个有点扭曲的四面体构型。在配合物中,H2LCl配体含有能够旋转的-CH_(2)-基团和联苯的结构,-CH_(2)-基团使得两个吡啶环与联苯环不在同一个平面上且两个吡啶环的方向相反使得配体呈现出“Z”字型结构,更能够让配体参与配位。另外,联苯中的π共轭结构不仅让每个一维链状配合物通过π-π堆积作用进一步形成三维超分子,还能增加其结构的稳定性。A Zn(II)complex,{[Zn(L)Cl_(2)]·4H_(2)O},was successfully constructed by using a semi rigid pyridinium polycarboxylic acid ligand 1,1’-([1,1’-biphenyl]-4,4’-diylbis(methylene))bis(4-carboxypyridin-1-ium)(H2LCl)as a linker and reacting with Zn2+ions under hydrothermal conditions at 120℃ for 72 hours.Through X-ray single crystal diffraction analysis,it was found that{[Zn(L)Cl_(2)]·4H_(2)O}is a one-dimensional chain structure,belonging to a monoclinic system.The P21/c space group(cell parameters a=15.951(6)Ẳ,b=9.636(4)Ẳ,c=18.849(7)Ẳ,α=90°,β=113.240(6)°,γ=90°).The Zn(II)center connects two carboxyl oxygen atoms and two Cl-ions in a four coordinated mode to form a slightly twisted tetrahedral configuration.In the complex,the H2LCl ligand contains a rotating-CH_(2)-group and a biphenyl structure.The-CH_(2)-group causes the two pyridine rings to be not in the same plane as the biphenyl ring,and the direction of the two pyridine rings is opposite,resulting in a“Z”shaped structure of the ligand,which is more conducive to the ligand’s participation in coordination.In addition,theπconjugated structure in biphenyls not only allows each one-dimensional chain like complex to further form three-dimensional supramolecules throughπ-πstacking,but also increases its structural stability.

关 键 词：吡啶鎓羧酸配体 Π-Π堆积作用 三维超分子 配位聚合物 晶体结构 

分 类 号：TQ[化学工程]