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  

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

作　　者：陈沛全[1,2] 孙宏伟[1] 陈兰[1] 沈荣欣[1] 袁满雪[1] 赖城明[1] 李正名[3] 

机构地区：[1]南开大学化学系 [2]南开大学元素有机化学研究所天津300071南开大学元素有机化学国家重点实验室天津300071南开大学科学计算研究所天津300071 [3]南开大学元素有机化学研究所

出　　处：《化学学报》2005年第13期1175-1181,i001,共8页Acta Chimica Sinica

基　　金：国家自然科学重点基金(No.29832050);教育部高等学校骨干教师资助计划;天津市科委高性能计算基金(04318511-5)资助项目

摘　　要：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.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 strong- est for β-chloro substitution. It has also been described that effect of β-halo substitution on host-guest inter- action from frequency analyses, NBO charge population, frontier orbital of interaction, dipole moment of activated conformation and Mulliken bonding population.

关 键 词：密度泛函理论 杯[4]吡咯 卤素取代 构象 主-客体相互作用 阴离子识别 超分子化学 

分 类 号：O626.13[理学—有机化学] O641.121[理学—化学]