First theoretical probe for efficient enhancement of optical nonlinearity via structural modifications into phenylene based D–π–A configured molecules

The design of nonlinear optical (NLO) materials using conjugated molecules via different techniques is reported in the literature to boost the use of these systems in NLO. Therefore, in the current study, designed phenylene based non-fullerene organic compounds with a D–π–A framework were selected for NLO investigation. The initial compound (PMD-1) was taken as a reference and its seven derivatives (PMDC2–PMDC8) were made by introducing different acceptor moieties into the chemical structure of PMD-1. To explain the NLO findings, frontier molecular orbital (FMO), transition density matrix (TDM), density of states (DOS), natural bond orbital (NBO) and UV-Vis study of the title compounds was executed by applying the PBE1PBE functional with the 6-311G(d,p) basis set. The descending order of band gaps (E(gap)) was reported as PMDC7 (2.656) > PMDC8 (2.485) > PMD-1 (2.131) > PMDC3 (2.103) > PMDC2 (2.079) > PMDC4 (2.065) > PMDC5 (2.059) > PMDC6 (2.004), in eV. Global reactivity parameters (GRPs) were associated with E(gap) values as PMDC6 with the lowest band gap showed less hardness (0.0368 E(h)) and high softness (13.5785 E(h)). The UV-Vis investigation revealed that the maximum λ(max) (739.542 nm) was exhibited by PMDC6 in dichloromethane (DCM) as compared to other derivatives. Additionally, natural bond orbital (NBO) based findings revealed that PMDC6 exhibited the highest stability value (34.98 kcal mol(−1)) because of prolonged hyper-conjugation. The dipole moment (μ), average linear polarizability 〈α〉, first hyperpolarizability (β(tot)) and second hyperpolarizability (γ(tot)) were evaluated for the reference and its derivatives. Consequently, among the designed compounds, the highest β(tot) (4.469 × 10(−27) esu) and γ(tot) (5.600 × 10(−32) esu) values were shown by PMDC6. Hence, it's concluded from said results that these structural modifications proved PMDC6 as the best second and third order NLO candidate for various applications like fiber optics, signal processing and data storage.