杯[4]二吡咯与卤素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] bipyrrole and Halide Anions

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

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

出　　处：《高等学校化学学报》2006年第2期332-335,共4页Chemical Journal of Chinese Universities

基　　金：国家自然科学重点基金(批准号: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(批准号:043185111-5)资助

摘　　要：采用密度泛函B3LYP方法,在6-31G*/LANL2DZ水平上对杯[4]二吡咯主体分子及其与卤素阴离子形成的复合物进行研究.结果表明,杯[4]二吡咯可与卤素阴离子相互作用形成具有较高对称性的复合物,其8个吡咯NH基团上的H原子均可以和卤素阴离子形成氢键;杯[4]二吡咯与卤素阴离子结合能力大小的顺序为F->C l->B r->I-.振动光谱、电荷分布以及前线轨道计算结果表明,杯[4]二吡咯与卤素阴离子相互作用的本质为氢键,经BSSE校正的结合能与电荷转移程度、N—H键键长和N—H伸缩振动频率变化呈线性关系.A new class of calix[ 4 ] pyrrole analogue containing bipyrrole show a good affinity for halide anions. calix[4] bipyrrole and its complexes with the halide anions were investigated by density functional theory （B3LYP） at the 6-31G^＊ and LANL2DZ level. It was shown that calix[4] bipyrrole and halide anions can form highly symmetric complexes by eight intermolecular hydrogen bonds. The interaction between calix [ 4 ] bipyrrole and halide anions decreased along the halide elemental period. The calculated results of frequency, charge distribution and front molecular orbital show that there are linear correlations between the BSSE correct binding energy and charge transference, N-H bond length, N-H stretch frequency shifts.

关 键 词：密度泛函(DKT) 二吡咯 卤素阴离子 主客体相互作用 氢键 

分 类 号：O641[理学—物理化学]