Computational and spectroscopic studies of biologically active coumarin-based fluorophores

We used density functional theory (DFT) calculations to examine the various molecular properties of two coumarin derivatives, namely 4-(5-amino-[1,3,4]thiadiazol-2-ylsulfanylmethyl)-7-methyl-chromen-2-one and 4-(5-amino-[1,3,4]thiadiazol-2-ylsulfanylmethyl)-7-methoxy-chromen-2-one at different levels of theory and basis sets. The calculated highest occupied molecular orbital and lowest unoccupied molecular orbital energies revealed that the investigated molecules were chemically active with a tendency for molecular interactions. The theoretical vibrational frequencies of these molecules were found to be consistent with the experimentally obtained frequencies. Moreover, solvatochromic measurements indicated no significant change in absorption spectral peak by varying the polarity of solvent. Under the same conditions we found that there was a red shift of 39 nm in the fluorescence spectral peak with increase in solvent polarity. The solvatochromic data were used to estimate excited dipole moments and the change in dipole moment was interpreted based on resonance structure of molecules.