Effects of the Nature and Length of the π‐Conjugated Bridge on the Second‐Order Nonlinear Optical Responses of Push–Pull Molecules Including 4,5‐Dicyanoimidazole and Their Protonated Forms

Abstract

Theoretical and experimental methods of characterization have been employed to investigate a series of six push-pull molecules containing a 4,5-dicyanoimidazole acceptor (A) unit, a N,N-dimethylamino donor (D) group, and systematically enlarged π-conjugated linkers (π) with the view of assessing their first hyperpolarizabilities (β) as well as their variations upon protonation. The results demonstrated that protonation occurred at the N,N-dimethylamino function, which led to disruption of the electronic charge-transfer delocalization: the A-π-D pattern of the neutral species with large β values was transformed into an A-π-A' pattern, which displayed much smaller β values. This feature makes these systems applicable as pH-triggered nonlinear optics (NLO) switches. In particular, protonation led to a decrease of the hyper-Rayleigh scattering first hyperpolarizabilities by at least one order of magnitude as well as to a decrease of the depolarization ratio, from about five for neutral species, which also supported the 1D-like NLO-phore nature, to about two for the protonated ones.