Modulation of the optical properties of D-π-A type azobenzene derivatives by changing the π-conjugated backbones: A theoretical study

Abstract

The optical properties of two series of azobenzene derivatives were modulated by backbone modifications with the density functional theory (DFT) calculations. Compared to the short-chain molecule, the chromophore with an elongated π-bridge exhibits a greater extent of charge transfer during one-photon excitation and hence possesses a larger molecular first hyperpolarizability (β0). Meanwhile, an evident red-shift in the maximum absorption was observed after extension of the π-conjugated backbone. The tendency of the static β0 value derived from the two-state model is consistent with the result of the calculation at M06-2X/6–311++G(d,p) level by means of analytical derivative method. The dynamic perturbations were revealed to cause the obvious enhancement of the first hyperpolarizability. The more closer the foundational wavelength to two times the value of the maximum absorption in one-photon transition, the larger βRHS value is observed for the chromophore. The nonlinear optical (NLO) properties augment with the introduction of the THF solvents by comparing the gas-phase values. With increasing the length of conjugated bridge, the dynamic βRHS value increases more rapidly in THF solution than in vacuum.