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本文设计了基于5,10,15-三(五氟苯基)corrole分子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(1α-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～-12.69 kJ/mol之间,而(1b)_2和(2b)_2的堆积作用能则分别增至-52.34 kJ/mol和-80.70 kJ/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.以上结果说明,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.
In this paper, a series of alkyl and aryl-substituted corrole (1α-4a) based on 5, 10, 15-tris (pentafluorophenyl) (1b-4b). The geometric optimization of the monomer was carried out on the basis of density functional theory (RB3LYP) at 6-31G ~ * level, and the electrostatic potential energy and charge distribution of the complexes were also analyzed.Using RHF / STO- The results of single point energy calculations for the aggregates of the four geometries of parallel sandwich, anti-parallel sandwich, parallel dislocation and parallel oblique dislocation show that the anti-parallel sandwich structure of these π-π stacking conformations Is the best way to pile up.The better π-π stacking geometry can be geometrically optimized by the RHF / STO-3G method for the anti-parallel stacking configuration. The free corrole 3a and 4a dimers have no packing effect, while the other two free corrole and copper complex dimers show a certain π-π stacking effect. The π-π stacking effect of dimers (1a) _2, (2a) _2, (3b) _2 and (4b) _2 can be between -4.47 and -12.69 kJ / mol, ) _2 increased to -52.34 kJ / mol and -80.70 kJ / mol, respectively. (1b) _2 and (2b) _2 showed significant strong π-π stacking mainly due to its pentafluorobenzene The electrostatic interaction exists between the fluorine atom in the base and the central metal copper.The above results show that the π-π stacking effect of corrole and its copper complex is not strong, while the substitution of the central alkyl group will make its π-π stacking effect Weaker.