三苯基Corrole及其铜配合物的π-π堆积效应研究  

Study on the π-π Stacking Effect of Tri-phenyl Corrole and Its Copper Complex

作　　者：刘海洋[1] 郭平叶[1] 徐志广[1] 应晓[2] 江焕峰[1] 张启光[3] 

机构地区：[1]华南理工大学化学系,广州510641 [2]华南理工大学应用物理系,广州510641 [3]香港科技大学化学系

出　　处：《无机化学学报》2007年第3期504-508,共5页Chinese Journal of Inorganic Chemistry

基　　金：国家自然科学基金(No.20332030;20572027);香港研究资助局和教育部留学回国科研启动基金资助

摘　　要：Aggregation behavior of 5,10,15-tris(pentafluorophenyl)corrole (F15TPC), 5,10,15,20-tetra(pentafluoroph-enyl)porphyrin (F20TPP), and their copper complexes in DCM solution were investigated by using UV-Vis spectro-scopic method. F20TPP and F20TPPCu exhibited strong π-π stacking interactions in DCM, and the intermolecular dimerization constants turned out to be 1.82 × 103 and 17.2 × 103 L·mol-1 respectively. However, extinction coefficients of F15TPC and F15TPCCu at soret band remained unchanged with increasing in their concentrations from 1.0 to 40.0 μmol·L-1, indicating they remained monomeric in DCM solution. Based on DFT calculation and the π-π stacking geometries observed in crystal structures of metal octaethylcorrole complexes, destroy of π-π interactions in F15TPC and F15TPCCu may be understood by the electrostatic potential surfaces (EPS) features of the molecules and steric repulsions caused by the introducing of three phenyl at the meso- positions of corrole macrocycle.Aggregation behavior of 5,10,15-tris（pentafluorophenyl）corrole （F15TPC）, 5,10,15,20-tetra（pentafluorophenyl）porphyrin （F20TPP）, and their copper complexes in DCM solution were investigated by using UV-Vis spectroscopic method. F20TPP and F20TPPCu exhibited strong π-π stacking interactions in DCM, and the intermoleeular dimerization constants turned out to be 1.82 × 10^3 and 17.2 × 10^3 L·mol^-1 respectively. However, extinction coefficients of F15 TPC and F15TPCCu at soret band remained unchanged with increasing in their concentrations from 1.0 to 40.0 u mol·L^-1, indicating they remained monomeric in DCM solution. Based on DFT calculation and the π-π stacking geometries observed in crystal structures of metal oetaethyleorrole complexes, destroy of π-π interactions in F15TPC and F15TPCCu may be understood by the electrostatic potential surfaces （EPS） features of the molecules and sterie repulsions caused by the introducing of three phenyl at the meso- positions of eorrole macrocycle.

关 键 词：卟啉 CORROLE 铜配合物 π-π堆积效应 DFT 

分 类 号：O614.121[理学—无机化学]