两种铜配位聚合物的晶体结构和量子化学计算  

Two Copper Coordination Polymers:Crystal Structure and Quantum Chemistry Calculation

作　　者：付立海 李秀梅 刘博[2] 周实[2] FU Li‑Hai;LI Xiu‑Mei;LIU Bo;ZHOU Shi(Faculty of Chemistry,Tonghua Normal University,Tonghua,Jilin 134002,China;Faculty of Chemistry,Jilin Normal University,Siping,Jilin 136000,China)

机构地区：[1]通化师范学院化学学院,通化134002 [2]吉林师范大学化学学院,四平136000

出　　处：《无机化学学报》2022年第11期2249-2258,共10页Chinese Journal of Inorganic Chemistry

基　　金：吉林省科技发展计划(No.20210101117JC)资助。

摘　　要：在水热条件下以4-硝基邻苯二甲酸(4-H_(2)nph)/2,2’-联吡啶-4,4’-二甲酸(H_(2)bda)为主要配体,3-(2-吡啶基)吡唑(HL)/1,4-双(咪唑基-1-基)丁烷(bib)为辅助配体制备了2种新的金属有机配位聚合物[Cu_(4)(4-nph)(L)_(6)]_(n)(1)和{[Cu_(2)(bda)_(2)(bib)_(2)(H_(2)O)_(4)]·4H_(2)O}_(n)(2)。通过元素分析、红外光谱、热重X射线单晶衍射和X射线粉末衍射对它们进行了表征。结果表明,配合物1属于单斜晶系,C2/c空间群。晶胞参数:a=1.956 16(8) nm,b=1.290 68(8) nm,c=2.160 34(12) nm,β=97.073(2)°,V=5.412 9(5) nm~3,Z=4。配合物2属于三斜晶系,P1空间群。晶胞参数:a=0.962 22(15) nm,b=1.102 90(17) nm,c=1.404 3(2) nm,α=72.752(4)°,β=79.271(4)°,γ=67.065(3)°,V=1.306 6(4) nm~3,Z=1。在配合物1中,羧基配体4-nph^(2-)通过单齿模式桥联金属中心,形成一维结构。在配合物2中,柔性bib配体连接金属中心形成具有26元环的双核结构。此外,还用Gaussian16程序PBE0/LANL2DZ方法从配合物1的晶体结构中提取“分子片段”进行了量子化学计算。计算结果表明配位原子与铜(Ⅱ)离子之间存在着共价作用。Two new metal-organic coordination polymers [Cu_(4)(4-nph)(L)_(6)]_(n)(1) and {[Cu_(2)(bda)_(2)(bib)_(2)(H_(2)O)_(4)]·4H_(2)O}_(n)(2) were prepared under hydrothermal conditions by employing 4-nitrophthalic acid(4-H2nph)/2,2’-bipyridine-4,4’-dicarboxylic acid(H2bda) as the primary ligand and 3-(2-pyridyl)pyrazole(HL)/1,4-bis(imidazol-1-yl)-butane(bib)as the ancillary ligand.They were characterized by elemental analysis,infrared spectroscopy,thermogravimetry,X-ray single crystal diffractometer,and X-ray powder diffractometer.The results show that complex1belongs to monoclinic system,C2/c space group with cell parameters:a=1.956 16(8) nm,b=1.290 68(8) nm,c=2.160 34(12)nm,β=97.073(2)°,V=5.412 9(5) nm3,Z=4;and complex2crystallizes in triclinic system,P1 space group with cell parameters:a=0.962 22(15) nm,b=1.102 90(17) nm,c=1.404 3(2) nm,α=72.752(4)°,β=79.271(4)°,γ=67.065(3)°,V=1.306 6(4) nm3,Z=1.In complex1,the carboxyl ligand 4-nph^(2-)bridges the metal centers via monodentate modes.The metal centers are coordinated by 4-nph^(2-)to form a 1D structure.In complex2,the flexible bib linked metal centers to form a dinuclear structure with a 26-member ring.In addition,the quantum-chemical calculations were accomplished on“molecular fragments”extracted from the crystal structure of 1 using the PBE0/LANL2DZ method in the Gaussian 16 program.The calculation values denoted the distinct covalent interaction between the coordinated atoms and Cu(Ⅱ) ion.CCDC:2130919,1;2097002,2.

关 键 词：配位聚合物 水热合成 晶体结构 量子化学 

分 类 号：O614.121[理学—无机化学]