SC-XRD structural characterization, insights of key electronic, and nonlinear optical properties of dimethoxybenzenesulfonate crystals: A combine experimental and DFT approach

•(MDBS, EDBS and DBSC) were prepared and crystallized.•Single crystal XRD were used for the characterization of title derivatives.•The key-electronic and NLO properties were investigated following M06/6-311G(d,p) functional of DFT/TDDFT approaches.•A good concurrence is observed between experimental and DFT findings.•Global reactivity descriptors were examined using HOMO/LUIMO energies.•Hyperpolarizability and second order hyperpolarizability were investigated for DBSC. Currently, dimethoxybenzene sulfonyl-based crystals (MDBS, EDBS and DBSC) were synthesized by in situ nucleophilic substitution reactions and their structures were confirmed via SC-XRD analysis. The key-electronic and NLO properties of afore-said crystals were investigated through quantum chemical study. For this purpose, M06/6-311G(d,p) functional of DFT/TDDFT approaches was utilized. A comparative study between DFT and XRD values of gemeterical parameters shwed harmony.Frontier molecular orbital findings revealed that among synthesized crystals, DBSC showed lesser energy (4.18 eV) with more red shift (322.758 nm) than MDBS (5.306 eV) and EDBS (5.320 eV). Global reactivity parameters (GRPs) were also examined from the energies of HOMO/LUMO. Among all crystals EDBS had higher value of hardness (η = 2.660 eV) while DBSC showed higher global softness (σ=0.240 eV) that indicated greater polariziability and interamolecular charge transfer in DBSC. The decreasing order of dipole moments of synthesized crystals was found as: DBSC (7.934 D) > MDBS (7.420 D) > EDBS (7.380 D). Further, from GRP it is revealed that MDBS-DBSC crystals having greater hardness values were less reactive and more stable as suggested by NBO and SC-XRD investigations. Owing to the unique properties of DBSC, significant NLO properties: hyperpolarizability (βtot=1.30 × 10−30esu) and second-order hyperpolarizability (γtot=22.1 × 10−36esu) were investigated in this crystal. The efficient NLO properties observed in DBSC underscore its potential use for advanced NLO applications. [Display omitted]