三苯基Corrole及其铜配合物的π-π堆积效应研究

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.

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