High-throughput virtual screening of organic second-order nonlinear optical chromophores within the donor–π-bridge–acceptor framework

Abstract

In view of the theoretical importance and huge application potential of second-order nonlinear optical (NLO) materials, it is of great significance to conduct high-throughput virtual screening (HTVS) on a compound library to find candidate NLO chromophores. Under the donor–π-bridge–acceptor structural framework, a virtual compound library (size = 27 090) was constructed by enumeration of structural fragments. The kernel property adopted for optimization is the static first hyperpolarizability (β₀). By combining machine learning and quantum chemical calculations, we have performed an HTVS procedure to sieve NLO chromophores out, and the response mechanism of the selected optimal NLO chromophores was examined. We have found: (a) The multi-layer perceptron/extended connectivity fingerprint combination with 20% selection ratio gives the highest prediction accuracy for the studied systems. (b) The two optimal donors are bis(4-diphenylaminophenyl)aminyl and bis(4-tert-butylphenyl)aminyl; the optimal π-bridges are composed of two thiophenyl, selenophenyl or furanyl units; and the two optimal acceptors are tri-s-triazinyl and 2,3-dicyanopyrazinyl. (c) The no. 1 candidate molecule can exhibit a calculated β₀ equal to 8.55 × 10⁴ a.u. (d) The difference in NLO responses of the optimal 16 molecules comes from the synergistic interaction of E_S1, Δμ and f, by employing the two-level model. In addition, the sizable Δμ and f allow the studied optimal molecules to obtain a large NLO response in the meantime keeping a not-too-low excitation energy (retaining good optical transparency in the restricted range of the visible spectrum region). (e) With further modification on the acceptor, the designed DPA-π-TRZ-A′ (A′ = CN or NO₂, π = oligo-thiophenyl or selenophenyl) systems can exhibit a rather large NLO response (maximum β₀ = 3.17 × 10⁵ a.u.), hence should have considerable potential as second-order NLO chromophores. With the above observations, we expect to provide some insight for the research community into the HTVS of organic second-order NLO chromophores.