NLO properties of ester containing fluorescent carbazole based styryl dyes - Consolidated spectroscopic and DFT approach

The linear and nonlinear optical (NLO) properties of new fluorescent styryl dyes based on anchoring ester containing carbazole as donor appended to different acceptor groups to have a conjugated pi-system with push-pull geometry are studied. The NLO properties have been determined using solvatochromic and computational methods. Three different TD-DFT functional are used namely, B3LYP, BHandHLYP, and CAM-B3LYP, with aim of elucidating better functional for NLOphores. Further, the two photon properties (sigma(2pA)) have been described theoretically by two level model considering the dipole moment difference between the ground and the final electronic states and bypassing the intermediated resonance state. The compounds with a high charge transfer from the acceptor group to the carbazole ring have relatively high two-photon absorption cross-sections (60-317 GM). The linear polarizability (alpha(CT)), first order hyperpolarizability (beta) and second order hyperpolarizability (gamma) for 4c dye was the highest among the studied dyes which is attributed to the lesser energy gap evident by both the methods. But in contrary, the sigma(2pA) cross-section value was low for dye 4c which is due to the presence of freely rotatable twisted phenyl ring in the conjugation path, pulling the electron density towards itself and thus lead to decrease in sigma(2pA) cross-section. Structure-property relationship is better understood by the correlation of bond length alternation/bond order alternation (BLA/BOA) with NLO properties of dyes. Thus by simple solvatochromic method and computational method, we have screened the carbazole styryls as NLO candidates with good first order hyperpolarizability and good two photon cross-section. (C) 2017 Elsevier B.V. All rights reserved.