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化学学报
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化学学报 ›› 2008, Vol. 66 ›› Issue (1): 31-38. 上一篇    下一篇

研究论文

β-三氰基乙烯取代杯[4]吡咯与阴离子相互作用的密度泛函理论研究

王腾 李琼 陈沛全 孙宏伟 陈兰 沈荣欣 赖城明   

  1. 南开大学化学系
  • 投稿日期:2007-01-16 修回日期:2007-08-01 发布日期:2008-01-14
  • 通讯作者: 孙宏伟

Density Functional Theory Studies on Interaction Between Calix[4]pyrrole Substituted by Tricyanoethylene on β Position and Anions

WANG Teng LI Qiong CHEN Pei-Quan SUN Hong-Wei* CHEN Lan SHEN Rong-Xin LAI Cheng-Ming   

  1. (Department of Chemistry, Nankai University, Tianjin 300071)
  • Received:2007-01-16 Revised:2007-08-01 Published:2008-01-14
  • Contact: SUN Hong-Wei

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采用密度泛函B3LYP方法对β-三氰基乙烯取代杯[4]吡咯主体分子及其与阴离子(F-、Cl-、CH3COO-、H2PO4-)形成的复合物进行研究。结果表明，β-三氰基乙烯取代杯[4]吡咯可与阴离子以分子间氢键相互作用形成复合物，并且其与阴离子结合能力大小的顺序为F-> CH3COO-> H2PO4-> Cl-，与实验结果基本一致；通过与杯[4]吡咯对比可见，强吸电子取代基的引入增强了主体分子对阴离子的结合能力。本文还从几何构型、振动光谱、NBO分析及前线轨道等方面来阐述β-三氰基乙烯取代杯[4]吡咯与不同阴离子氢键相互作用的本质以及吸电子取代基的引入对杯[4]吡咯与F-和Cl-之间主-客体相互作用的影响。

关键词: β-三氰基乙烯取代杯[4]吡咯, 阴离子识别, 主-客体相互作用, 氢键

Density functional theory has been performed on the calix[4]pyrrole substituted by tricyanoethylene and its complexes with the anions(F-、Cl-、CH3COO-、H2PO4-). It was shown that the host and anions could form complexes by intermolecular hydrogen bonds, and the order of the binding affinity for host is as follows : F-> CH3COO-> H2PO4-> Cl-, which is in good agreement with the experimental values; To contrast with the interaction between calix[4]pyrrole and F- and Cl-, the electron – withdrawing group substitution can enhance the interaction between calix[4] pyrrole and F- and Cl-. It has also been described that the different interaction between host and the anions and the effect of electron – withdrawing group substitution on host-guest interaction from geometry features, frequency analyses, NBO analyses and frontier orbital of interaction.

Key words: β-tricyanoethylene substituted calix[4]pyrrole, anion recognition, host-guest interaction, hydrogen bond