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

The geometric and electronic absorption spectra and second-order nonlinear optical (NLO) properties of 5, 15-bis(pentafluorophenyl)-10-(2-aminophenyl) corrole (F₁₀Cor) 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 coefficients β₀ for F₁₀Cor and complexes followed an order of F₁₀CorCu(57.75×10^-30 esu), F₁₀Cor(37.92×10^-30 esu), F₁₀CorMn(27.10×10^-30 esu) and F₁₀CorGa(20.00×10^-30 esu), the second-order NLO responses of these compounds were mainly contributed by the β_y component. The second-order NLO responses of the F₁₀CorCu complex were derived from the β-HOMO-1 to β-LUMO transition, exhibiting intraligand charge transfer (ILCT) transition between 2-aminophenyl and corrole macrocycle. The calculations of the dynamic first hyperpolarizability indicated that F₁₀Cor and all metal complexes have not shown strong dispersion effect under the influence of incident wavelength of 1 907 nm. The dynamic second-order NLO coefficients (β_{1 907 nm}) were about twice as large as static β₀ values, following an order of F₁₀CorCu (103.94×10^-30 esu), F₁₀Cor (60.60×10^-30 esu), F₁₀CorMn(48.75×10^-30 esu) and F₁₀CorGa(34.39×10^-30 esu).