A DFT study of the second-order nonlinear optical properties of [22]smaragdyrin-BF2-NiII porphyrin fused hybrids.

[Display omitted] • The relationship between the structure and NLO property of [21]smaragdyrin-BF 2 -Ni^II porphyrin fused hybrids was investigated. • The P S P fused hybrids show larger NLO response as compared to S P fused hybrids. • HRS hyperpolarizability of the complex at λ = 1907 nm is higher than the static value. Nonlinear optical response of four [22]smaragdyrin-BF 2 (S)-Ni^II porphyrin (P) fused hybrids were explored by using DFT at CAM-B3LYP/6–31 + G(d)/SDD level of theory. We choose two types of hybrids, S P and P S P fused hybrids, for our study. Calculations indicate that these fused hybrids might be promising candidates for NLO materials based on considerable static and dynamic hyper-Rayleigh scattering (HRS) hyperpolarizability. The P S P fused hybrids possess larger first hyperpolarizabilities values compared to S P hybrids. Further analysis of hyperpolarizability density reveals the nature of the large first hyperpolarizability of the P S P fused hybrids. For all compounds, HRS hyperpolarizability at λ = 1907 nm is higher than the static value. After the interpretation of dipolar and octupolar character of β HRS , these hybrids show the high dipolar character. [ABSTRACT FROM AUTHOR]