Theoretical investigation of substitution effect on the sixth and seventh positions of coumarin derivatives.

The linear and non-linear optical properties of 6-donor and 7-donor substituted coumarins were compared using density functional theory (DFT) and time-dependent-DFT (TD-DFT). Charge transfer characteristics were investigated through natural bond order analysis, frontier molecular orbital, and molecular electrostatic potential plots. TD-DFT results suggested that the 6-donor substituted coumarins (PS1, PS3, and PS5) showed red-shifted absorption than the 7-donor substituted coumarins (PS2, PS4, and PS6). The chemical potential (μ) and electrophilicity index (ω) showed direct relation with the band gap and an inverse relation with chemical hardness (η) and hyperhardness (Γ). The global reactivity descriptors μ and ω showed direct and η and Γ showed an inverse correlation with first-order hyperpolarizability (β) and second-order hyperpolarizability (γ). The β and γ for 7-donor substituted coumarin are higher than for 6-donor substituted coumarin.