【摘要】 采用密度泛函B3LYP/LanL2DZ方法优化了气相以及在四氢呋喃(THF)、甲醇及二甲亚砜(DMSO)3种溶剂中邻-二(吡咯-2-甲酰胺基)亚苯(DPCP)及其卤素阴离子复合物的几何构型。从几何结构、电荷布居、结合能以及热力学参数等角度探讨复合物形成过程中受体与阴离子间的相互作用。研究结果表明:复合物稳定性与卤素离子的种类和溶剂极性有关,同一溶剂中,复合物DPCP-X~-以DPCP-F~-最稳定,随着卤素离子半径的递增,稳定性逐渐下降,F~-,Cl~-在气相和3种溶剂中都能形成稳定的复合物,Br~-复合物只在气相稳定,在选定的3种溶剂中均不能形成稳定的复合物,而I~-无论在气相还是在3种溶剂中均不能形成稳定的复合物;同一复合物DPCP-X~-稳定性随溶剂极性的增大逐渐减小。利用相同的理论方法预测了在3种溶剂中DPCP与OH~-及CN~-的相互作用能力及复合物的稳定性。更多还原

【Abstract】 The structure of o-di-(pyrrole-2-carboxamides)-phenylene(DPCP) and its halide anion complexes were optimized by density functional theory B3LYP/LanL2DZ method.The bulk solvent effects are taken into account for the DFT calculation by means of the standard polarizable continuum model(PCM).The solute surrounded by the solvent represented by a polarizable continuum dielectric:DiMethylSulfoxide(DMSO), methanol(MeOH) and tetraHydroFuran(THF).The conformation change of the host and the supramolecular interaction between the host and halide anion,in the formation of complexes,have been investigated by analyzing the geometric parameters,charge population,binding energy and thermodynamic parameters.The results show that DPCP-F~- is the most stable among the complex DPCP1-X~-(X~-=F~-,Cl~-,Br~-,I~-),with comparable binding affinities.The calculated results agree well with the experimental results reported in the literature.The supramolecular interaction between the host and OH~- and CN~- anion were predicted with the same method.更多还原