LAUSR

Improvement in the first hyperpolarizability (βHRS) as well as intrinsic hyperpolarizability (βint) of chromophores based on 9,9-dimethyl-9H-fluoren-2-amine through modulation of the conjugation pathway is described. A series of six novel chromophores with “linear” conjugation showed significant enhancement of βHRS as well as βint compared to the counterparts lacking a “linear” conjugation but having an identical combination of donor, acceptor, and the intervening π-conjugated linker. The hyperpolarizability (βHRS as well as βint) values of the new series measured using hyper-Rayleigh scattering exceeded the apparent limit set by the latter set of fluorene-based chromophores. The experimental results are analyzed and interpreted in the context of linear optical properties, single-crystal X-ray analysis, electrochemistry, etc. and corroborated by theoretical studies. We find that modulation of the “push–pull” of the conjugation pathway in these donor–acceptor chromophores compares favourably with the corresponding changes in the optical gaps, transition dipole moments, and dipole moment difference between the ground and excited states.