臂式冠醚与碱金属Li^+,Na^+配合物结构与性能的理论研究(英文)

Theoretical Study on the Structure,Spectrum and Electronic Structures of Lariat Crown Ether-cation Complexes

基于N-丁基-氮杂15-冠-5母体环的一系列的不同端位取代基的臂式冠醚,用DFT//B3LYP/6-31G*方法进行计算讨论.气相中,金属配合物有两种稳定构型:"V"型的夹心结构(构型A)和线性的构型(构型B).另外,利用NBO分析和IR光谱的方法,理论上推断出主-客体配合物分子间的相互作用的电子结构本质.结果表明,气相中LCEs和金属阳离子(Li+和Na+)间的相互作用主要是离子-偶极作用,而阳离子-π电子的相互作用不明显.

A series of lariat crown ether based on N-butyl-aza-15-crown-5,which have the same parent macrocycle but with a different terminal group in sidearm,have been calculated at the DFT//B3LYP/6-31G＊ level in Gaussian 03 package program.The optimized geometries of two conformers （＂V＂-shaped sandwich conformer A and the linear structural conformer B） for their cation complex are obtained from theory in gas phase.In addition,the NBO analysis and the IR spectra inform the interaction between the hostguest molecules in detail.As a result,a conclusion obtained that the main interaction between the LCEs and cations （Li＋ and Na＋） is the cation-dipole,and the cation-π is not remarkable in gas phase.