Design of A-D-A-Type Organic Third-Order Nonlinear Optical Materials Based on Benzodithiophene: A DFT Study

The acceptor-donor-acceptor (A-D-A) type conjugated organic molecule has been widely applied in the organic optoelectronics field. A total of Nine compounds (1–9) were designed under the A-D-A framework, with the electron donor benzodithiophene as the core and dicyanomethylene as the acceptor moiety, modifying the benzodithiophene with the phenyl, naphthyl, and difluorinated phenyl groups. The conjugation length can be changed by introducing a thiophene π-conjugated bridge. The geometric structures, electronic structure, excited state properties, aromaticity, and the static- and frequency-dependent second hyperpolarizabilities were investigated by employing high-precision density functional theory (DFT) calculations with an aug-cc-pVDZ basis set. As a result, the three compounds with the longest conjugation length exhibit a smaller energy gap (E(gap)), larger UV-vis absorption coefficient, and response range, which are the three strongest third-order nonlinear optical (NLO) response properties in this work. This work systematically explored the connection between molecular structure and NLO response, which provides a rational design strategy for high-performance organic NLO materials.