Synthesis, spectroscopic, SC-XRD/DFT and non-linear optical (NLO) properties of chromene derivatives

In the present study, we reported the efficient synthesis of novel, heterocyclic, coumarin-based pyrano-chromene derivatives, 2-amino-8-methyl-5-oxo-4-[2-(2-oxo-2H-chromen-3-ylmethoxy)-phenyl]-4H,5H-pyrano[3,2-c]chromene-3-carbonitrile (4a) and 2-amino-8-methyl-5-oxo-4-[2-(2-oxo-2H-chromen-3-ylmethoxy)-phenyl]-4H,5H-pyrano[3,2-c]chromene-3-carboxylic acid methyl ester (4b). The chemical structures of synthesized compounds were resolved by employing various spectroscopic techniques like UV-Vis, FT-IR, (1)H & (13)C NMR, and single crystal X-ray diffraction (SC-XRD) analysis. The compounds; 4a and 4b, with appealing π-bonded skeleton were further analyzed in terms of their electronic and structural aspects using an integral approach of density functional theory (DFT) and time-dependent DFT (TD/DFT). The methodology: M06-2X/6-31G(d,p) level of theory was applied to compare their experimental data with theoretical outcomes using quantum chemical analysis. The frontier molecular orbitals (FMOs) study revealed that, 4a possesses a low band gap (5.168 eV) as compared to 4b (6.308 eV). Global reactivity parameters were associated with E(gap) values as 4a, with the lowest band gap showed the smaller value of hardness (0.094 eV) and a larger value of softness (5.266 eV). The non-linear optical (NLO) insight exhibited that, the average polarizability 〈α〉 and second hyperpolarizability (γ(tot)) were observed in 4a as 6.77005 × 10(−23) and 0.145 × 10(4) esu, respectively. Overall, the computational studies suggest that the investigated compounds have distinct NLO properties.