﻿ 芳香二磺酸根桥联的锌配位聚合物的合成、表征、晶体结构及量子化学计算

### 芳香二磺酸根桥联的锌配位聚合物的合成、表征、晶体结构及量子化学计算

1. 淮海工学院化学工程学院, 江苏 连云港 222005; 南京理工大学化工学院, 南京 210094
• 收稿日期:2009-10-13 修回日期:2009-12-06 发布日期:2010-03-03
• 通讯作者: 陆路德 E-mail:Lldnju@yahoo.com.cn

### Synthesis, Characterization, Crystal Structure and Quantum Chemistry Calculation of an Arenedisulfonate Bridged Zn(II) Coordination Polymer

QIAN Bao-Hua, MA Wei-Xing, LU Lu-De, YANG Xu-Jie, WANG Xin

1. School of Chemical Technology, Huaihai Institute of Technology, Lianyungang 222005, Jiangsu Province, P. R. China; School of Chemical Technology, Nanjing University of Science & Technology, Nanjing 210094, P. R. China
• Received:2009-10-13 Revised:2009-12-06 Published:2010-03-03
• Contact: LU Lu-De E-mail:Lldnju@yahoo.com.cn

ZnO与1,5-萘二磺酸在水溶液中反应, 再加入含咪唑的甲醇溶液合成得到新颖的锌配位聚合物{[Zn(C10H6O6S2)(C3H4N2)2(H2O)]·2H2O}n. 通过元素分析、红外光谱、核磁共振氢谱和热重分析等方法对配合物进行了表征. 通过X射线单晶衍射测得其晶体结构. 该配合物为三斜晶系, 空间群为P1, 晶体学参数: a=0.85313(19) nm, b=1.0253(2) nm, c=1.3357(3) nm, α=100.653(2)°, β=100.135(3)°, γ=108.859(2)°, V=1.0511(4) nm3, Dc=1.712 g·cm-3, Mr=541.85, Z=2, F(000)=556, μ=1.425 mm-1. Zn离子通过磺酸基团形成桥联配位, 进而构筑了二维(2D)的配聚物. 层间通过水分子的氢键作用构成了有序的三维(3D)超分子结构. 并运用Gaussian 03W对配合物结构单元进行了量子化学计算分析, 原子电荷分布及前线占据分子轨道组成很好地佐证了晶体结构的配位环境.

Abstract:

A novel zinc (II) coordination polymer {[Zn(C10H6O6S2)(C3H4N2)2(H2O)]·2H2O}n was synthesized by reacting ZnO, 1,5-naphthalenedisulfonic acid, and imidazole in H2O/MeOH solution. It was characterized by elemental analysis, infrared (IR) spectroscopy, 1H nuclear magnetic resonance (1H NMR) spectroscopy, and thermogravimetric analysis (TGA). The crystal structure was determined by single-crystal X-ray diffraction. The crystal belongs to the triclinic system with a P1 space group, and the crystallographic characteristics of the compound are: a=0.85313(19) nm, b=1.0253(2) nm, c=1.3357(3) nm, α=100.653(2)°, β=100.135(3)°, γ=108.859(2)°, V=1.0511(4) nm3, Dc=1.712 g·cm-3, Mr=541.85, Z=2, F(000)=556, μ=1.425 mm-1. The zinc ions are bridged by naphthalene-1,5-disulfonate anions, which forms a neutral two-dimensional (2D) coordination polymer. Hydrogen bonds that are generated by water molecules between the layers connect the layers to form a three -dimensional (3D) supramolecular structure. A theoretical investigation of the title complex as a structural unit was carried out using Gaussian 03W. The distribution of charges and the composition of the frontier molecular orbitals provided confirmation about the coordination
geometry of the crystal structure.