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.
出处
《化学学报》
SCIE
CAS
CSCD
北大核心
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
