Exploration of linear and third-order nonlinear optical properties for donor–π-linker–acceptor chromophores derived from ATT-2 based non-fullerene molecule

In the current study, seven non-fullerene compounds abbreviated as ATTD2–ATTD8 were designed through structural tailoring and their nonlinear optical (NLO) properties were reported. The objective of this study was to explore the potential for newly configured D–π–A type non-fullerene-based compounds. Quantum chemical methods were adopted and revealed the molecules as highly efficient materials with favorable NLO characteristics for use in optoelectronic devices. The M06 functional along with the 6-311G(d,p) basis set in chloroform solvent were utilized for the natural bonding orbital (NBO) analysis, absorption spectra and computational assessments of frontier molecular orbitals (FMOs), global reactivity descriptors (GRPs), transition density matrix (TDM) and nonlinear optical properties (NLO) for ATTR1 and ATTD2–ATTD8. The HOMO–LUMO energy gap was significantly reduced in all the designed moieties compared to the reference compound in the following decreasing order: ATTR1 > ATTD8 > ATTD4 > ATTD5 > ATTD2 > ATTD7 > ATTD6 > ATTD3. All of the designed molecules (ATTD2–ATTD8) showed good NLO response. Global reactivity parameters were found to be closely associated with the band gap between the HOMO and LUMO orbitals, and the compound with the smallest energy gap, ATTD3, exhibited a lower hardness value of 1.754 eV and higher softness value of 0.570 eV with outstanding NLO response. For the reference compound and ATTD2–ATTD8 derivatives, attributes like dipole moment (μ(tot)), average polarizability 〈α〉, first hyperpolarizability (β(tot)), and second hyperpolarizability γ(tot) were calculated. Out of all the derivatives, ATTD3 revealed the highest amplitude with a β(tot) of 8.23 × 10(−27) esu, which was consistent with the reduced band gap (1.754 eV) and suggested it was the best possibility for NLO materials in the future.