5,15-二(五氟苯基)-10-(2-氨基苯基)金属咔咯的二阶非线性光学性质

Second-Order Nonlinear Optical Properties of 5,15-Bis(pentafluorophenyl)-10-(2-aminophenyl)Metal Corrole

运用密度泛函理论(DFT)研究了5,15-二(五氟苯基)-10-(2-氨基苯基)咔咯(F10Cor)及其金属(Mn、Cu、Ga)配位化合物的几何结构、电子吸收光谱和二阶非线性光学(NLO)性质.利用态求和的方法在CAM-B3LYP/augcc-p VDZ水平计算了咔咯配位化合物的二阶NLO系数(β0).计算结果表明:F10Cor及配位化合物的静态二阶NLO系数β0的大小顺序为F10Cor Cu(57.75×10^-30esu)、F10Cor(37.92×10^-30esu)、F10CorMn(27.10×10^-30esu)、F10CorGa(20.00×10^-30esu),这些咔咯配位化合物的二阶非线性光学响应主要源自于βy分量的贡献.F10CorCu的二阶NLO响应主要来源于β-HOMO-1→β-LUMO轨道跃迁,表现为2-氨基苯基与咔咯大环之间的配体内电荷转移(ILCT)跃迁.动态第一超极化率计算结果表明,在波长为1907 nm入射光照下,F10Cor及金属配位化合物均未表现出强的色散效应,其动态二阶NLO系数(β(1907 nm))约为静态值β0的2倍,顺序为F10CorCu(103.94×10^-30esu)、F10Cor(60.60×10^-30esu)、F10CorMn(48.75×10^-30esu)、F10CorGa(34.39×10^-30esu).

The geometric and electronic absorption spectra and second-order nonlinear optical(NLO)properties of 5,15-bis(pentafluorophenyl)-10-(2-aminophenyl)corrole(F10 Cor)and metal corrole(Mn,Cu,Ga)complexes have been investigated with density functional theory(DFT)calculations.The second-order NLO coefficients(β0)of corrole complexes were calculated on the CAM-B3LYP/aug-cc-pVDZ level using the sum-over-states(SOS)method.The calculated results showed that the static second-order NLO coefficientsβ0 for F10 Cor and complexes followed an order of F10 CorCu(57.75×10^-30 esu),F10 Cor(37.92×10^-30 esu),F10 CorMn(27.10×10^-30 esu)and F10 CorGa(20.00×10^-30 esu),the second-order NLO responses of these compounds were mainly contributed by theβy component.The second-order NLO responses of the F10 CorCu complex were derived from theβ-HOMO-1 toβ-LUMO transition,exhibiting intraligand charge transfer(ILCT)transition between 2-aminophenyl and corrole macrocycle.The calculations of the dynamic first hyperpolarizability indicated that F10 Cor and all metal complexes have not shown strong dispersion effect under the influence of incident wavelength of 1907 nm.The dynamic second-order NLO coefficients(β1907 nm)were about twice as large as staticβ0 values,following an order of F10 CorCu(103.94×10^-30 esu),F10 Cor(60.60×10^-30 esu),F10 CorMn(48.75×10^-30 esu)and F10 CorGa(34.39×10^-30 esu).