中文摘要：

本文设计了基于5，10，15-三（血氟苯基）corrole分了中改变中位五氟苯基为丙基的一系列烷基和芳基中位取代的corrole（1a-4a）及其铜配合物（1b-4b）．用密度泛函方法（RB3LYP）在6—31G^＊基础水平上进行单体的几何优化，并对其静电势能和电荷分布进行了分析．用RHF／STO-3G方法对平行三明治，反平行三明治，平行错位和平行斜错位4种几何构型的二聚集体进行单点能计算，结果显示：在这几种π-π堆积构型中反平行三明治式结构是最好的堆积方式．更好的π-π堆积几何结构可以通过RHF／STO-3G方法对反平行堆积构型进行几何优化得到．自由corrole 3a和4a二聚体没有堆积作用，而其它的2个自由corrole和铜配合物二聚体则均表现出一定的π-π堆积作用．其中二聚体（1a）2，（2a）2，（3b）2和（4b）2的π-π堆积作用能在-4．47～-．12．69kJ／mol之间，而（1b）2和（2b）2的堆积作用能则分别增至-52．34kJ／mol和-80．70kJ／mol．（1b）2和（2b）2表现出显著的强π-π堆积作用，主要是因为其周边五氟苯基中的氟原子与中心金属铜之间存在静电作用．以E结果说明，corrole及其铜配合物的π-π堆积作用不强，而中位的烷基取代将使其π-π堆积作用变得更弱．

英文摘要：

A series of meso-aryl and alkyl substituted corroles （1a-4a） and their copper complexes were designed from the modification of 5,10,15-tris（pentafluoropheny）corrole by replacing meso-pentafluoropbenyl with n-propyl group. Then geometry optimization were performed by RB3LYP/6-31G^＊ method. Electrostatic potential surface map and charge distribution characteristics of designed corroles were also depicted. Single point energy of designed stacking geometries of parallel-sandwich, antiparallel-sandwich, parallel-displaced and parallel-slipped dimmeric aggregates of these corroles were calculated by RHF/STO-3G method. The results showed that the antiparallel-sandwich is the most optimal π-π stacking confirmation. Better π-π interaction confirmations could be further obtained by optimizing the constructed antiparallel-sandwich structures with RHF/STO-3G method. Free base corrole （3a）2 and （4a）2 exhibit no π-π interaction, while other free base corroles and all copper corrole complexes exhibit π-π interaction. The π-π interaction energies of copper corroles are larger than that of corresponding free base corroles. The π-π interaction energies of （1a）2, （2a）2, （3b）2 and （4b）2 vary from -4.47kJ/mol to -12.69 kJ/mol. The π-π interaction energies of （1b）2 and 2b）2 increased up to -52.34 kJ/mol and -80.70 kJ/mol respectively. The remarkable increasing of π-π stacking energies of （1b）2 and （2b）2 are caused by the electrostatic interaction between fluorine of pentafluorophenyl and central copper metal ion. These results show corrole and its copper complex exhibit weak π-π stacking interaction and the meso-alkyl substitution will further reduce the π-π interaction of corroles.