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  

Density Functional Theory Studies on Interaction between Calix[4]pyrrole Substituted by Tricyanovinyl at β-Position and Anions

作　　者：王腾[1] 李琼[1] 陈沛全[1] 孙宏伟[1] 陈兰[1] 沈荣欣[1] 赖城明[1] 

机构地区：[1]南开大学化学学院,天津300071

出　　处：《化学学报》2008年第1期31-38,共8页Acta Chimica Sinica

基　　金：国家高技术研究发展专项经费(No.2006AA10A213);南开大学"南开之星"高性能计算资助项目

摘　　要：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.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.Density functional theory has been performed on the tricyanovinyl substituted calix[4]pyrrole and its anion （F^-, Cl^-, CH3COO^-, H2PO4 ） complexes. The calculation results implied that the host-anion complexes were formed by intermolecular hydrogen bonds. The order of the binding affinity： F 〉CH3COO-〉 H2PO4 〉Cl-, was in good agreement with the experimental result. The electron-withdrawing group substitution would enhance the interation between the calix[4]pyrrole and anions. The effect of tricyanovinyl substitution on host-guest interaction from geometry features, frequency analyses, NBO analyses and frontier orbitals of interaction has also been described.

关 键 词：吡咯 阴离子识别 主-客体相互作用 氢键 

分 类 号：O621.1[理学—有机化学]