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化学学报
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化学学报 ›› 2007, Vol. 65 ›› Issue (21): 2377-2381. 上一篇    下一篇

研究论文

密度泛函理论研究DMSO溶剂中邻-二(吡咯-2-甲酰胺基)亚苯与卤素阴离子间的超分子作用

潘国祥，倪哲明*，王力耕，李小年   

  1. (浙江工业大学化学工程与材料学院催化新材料研究所 杭州 310032)
  • 投稿日期:2006-12-05 修回日期:2007-02-07 发布日期:2007-11-14
  • 通讯作者: 倪哲明

A DFT Study on Supramolecular Interaction between Halide Anion and o-Di(pyrrolyl-2-formamido)phenylene in DMSO

PAN Guo-Xiang; NI Zhe-Ming*; WANG Li-Geng; LI Xiao-Nian   

  1. (Laboratory of Advanced Catalytic Materials, College of Chemical Engineering and Materials Science, Zhejiang University of Technology, Hangzhou 310032)
  • Received:2006-12-05 Revised:2007-02-07 Published:2007-11-14
  • Contact: NI Zhe-Ming

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1026

被引次数

25

采用混合密度泛函B3LYP方法, 在LANL2DZ水平上优化DMSO溶剂中邻-二(吡咯-2-甲酰胺基)亚苯(PFP)及其卤素阴离子复合物的几何构型, 从几何结构参数、电荷布居、前线轨道、结合能以及热力学参数等角度探讨复合物形成过程中主体分子的构象变化以及主客体间的超分子作用. 研究结果表明, 邻-二(吡咯-2-甲酰胺基)亚苯识别卤素阴离子是一个自发过程. 复合阴离子过程中, 两者的前线轨道发生作用, 电子容易从卤素阴离子的HOMO向主体分子的LUMO转移. 在所形成的四种复合物PFP:X－(X－＝F－, Cl－, Br－, I－)中, 以PFP:F－最稳定, 与文献报道邻-二(吡咯-2-甲酰胺基)亚苯识别卤素阴离子能力的实验结果相一致. 设计合成含多个吡咯酰胺基团、并能形成合适“杯口”大小的主体化合物, 将增强对卤素阴离子的识别能力.

关键词: 邻-二(吡咯-2-甲酰胺基)亚苯, 阴离子识别, 密度泛函理论

The structures of o-di(pyrrolyl-2-formamido)phenylene (PFP) and its halide anion complex in DMSO were optimized by density functional theory B3LYP method at the LANL2DZ level. The conformation change of the host and the supramolecular interaction between the host and the halide anion, in the formation of the complex, have been investigated by analyzing the geometric parameters, charge population, frontier orbital, binding energy and thermodynamic parameters. The results show that anion recognition of PFP is spontaneous. The frontier orbital of the host interacts with that of the guest anion in the formation of the complex, and the electron is transferred from HOMO of halide anion to LUMO of the host. Moreover, PFP:F－ is most stable among the complexes PFP:X－ (X－＝F－, Cl－, Br－, I－), which agrees well with the experimental results of anion recognition of PFP reported in the literature. At last, if a host molecule con-taining multi-groups of pyrrolyl-2-formamido with the size of cup-shaped meatus appropriately regulated can be designed, the halide anion recognition of the host molecule will be improved.

Key words: o-di(pyrrolyl-2-formamido)phenylene, anion recognition, density functional theory