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化学学报
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化学学报 ›› 2005, Vol. 63 ›› Issue (13): 1175-1181. 上一篇    下一篇

研究论文

β-卤素取代对杯[4]吡咯构象及主-客体相互作用的影响II. 密度泛函理论研究

陈沛全abcd，孙宏伟*ad，陈兰1，沈荣欣11，赖城明1 2，李正名bcd   

  1. (1南开大学化学系 天津 300071)
    (2南开大学元素有机化学研究所 天津 300071)
    (3南开大学元素有机化学国家重点实验室 天津 300071)
    (4南开大学科学计算研究所 天津 300071)
  • 投稿日期:2004-11-23 修回日期:2005-03-17 发布日期:2010-12-10
  • 通讯作者: 孙宏伟

Effects on the Conformations and Host-guest Interaction of Calix[4]pyrroles Substituted by Halide on β Positions II. Density Functional Theory Study

CHEN Pei-Quanabcd, SUN Hong-Wei*ad, CHEN Lan1, SHEN Rong-Xin1, YUAN Man-Xue1, LAI Cheng-Ming1,2, Li Zheng-Mingbcd   

  1. (1 Department of Chemistry, Nankai University, Tianjin 300071)
    (2 Institute of Elemento-Organic Chemistry, Nankai University, Tianjin 300071)
    (3 State Key Laboratory of Elemento-Organic Chemistry, Nankai University, Tianjin 30007)
    (4 Institute of Scientific Computing, Nankai University, Tianjin 300071)
  • Received:2004-11-23 Revised:2005-03-17 Published:2010-12-10
  • Contact: SUN Hong-Wei

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应用密度泛函理论对杯[4]吡咯及卤素取代杯[4]吡咯模型分子的自由主体以及其卤素离子复合物体系进行计算研究. 结果表明, 杯[4]吡咯β位被卤素拉电子基团取代后, 主体分子的构象特征受吡咯单元的偶极影响; β-卤素取代导致了杯[4]吡咯对卤素离子的结合作用增强, 且当β位为氯取代时, 杯[4]吡咯对卤素离子的结合能力最强. 并从振动光谱、NBO电荷布居、相互作用的前线轨道、“活性”构象的偶极矩和Mulliken成键布居等方面阐述β-卤素取代对杯[4]吡咯与卤素离子之间的主-客体相互作用的影响.

关键词: 杯[4]吡咯, 阴离子识别, β-卤素取代, 主-客体相互作用

Density functional theory has been performed on the free host and its halide anion complexes of calix[4]pyrrole and halide substituted calix[4]pyrroles. The calculated result implied that the conformation feature of host is mainly due to pyrrole unit dipole moment. The result also indicated that β-halo substitution would enhance the interaction between calix[4]pyrrole and halide anion, and the interaction was the strongest for β-chloro substitution. It has also been described that effect of β-halo substitution on host-guest interaction from frequency analyses, NBO charge population, frontier orbital of interaction, dipole moment of activated conformation and Mulliken bonding population.

Key words: calix[4]pyrrole, anion recognition, β-halo substitution, host-guest interaction