Density functional theory prediction for the second-order nonlinear optical responses of phenanthroline-fused phthalocyanine derivatives

Abstract

A series of unsymmetrical phenanthroline-fused phthalocyanine derivatives including Zn [ Pc ( Phen )], Zn [ Pc ( Phen )2], Zn [ Pc ( Phen )3], Zn [ Pc ( NH 2)6( Phen )], Zn [ Pc ( NH 2)4( Phen )2], Zn [ Pc ( NH 2)2( Phen )3], Zn [ PcF 6( Phen )], Zn [ PcF 4( Phen )2], and Zn [ PcF 2( Phen )3] were designed to explore their properties of geometric and electronic structures, electronic absorption spectra, and second-order nonlinear responses under density functional theory and time-dependent density functional theory calculations. The computational results show that the peripheral substituents with push-pull effect could obviously change the π–π* transitions, leading to a tunable absorption region in the range between 300–800 nm. The hyperpolarizabilities were carefully investigated using CP-DFT method, revealing the size effect and clarifying the limit when expanding the conjugated system is employed to improve the hyper-Rayleigh scattering response coefficient (βHRS). According to the results, the NH 2-substitued phenanthroline-fused phthalocyanines are considered as ideal NLO blocking materials with large βHRS.