Unveiling the effects of atomic electronegativity on the ESIPT mechanism and luminescence property of new coumarin benzothiazole Fluorophore: A TD-DFT exploration

The excited-state intramolecular proton transfer (ESIPT) mechanism, photophysical properties of 8-(benzo[D] thiazole-2-yl)-7-hydroxy-2H-benzopyran-2-one (L-HKS) and the effect of O/Se atomic substitution on L-HKS have been studied in detail based on density functional theory (DFT) and time-dependent DFT (TD-DFT) methods. The S atom in the thiazole ring of L-HKS has been replaced by O/Se atom (denoted to L-HKO/L-HKSe) to analyze the effects of atomic electronegativity on the intramolecular H-bond, absorption/emission spectrum and ESIPT process. Through the analysis of series of calculated results, it can be found that the intramolecular H-bonds at normal form and tautomer form are enhanced and weakened in the S1 state, respectively, which is favorable to ESIPT process. The potential energy curves revealed that the ESIPT process is much easier to occur gradually from L-HKO to L-HKS and L-HKSe, as the electron-withdrawing ability of atom (from O to S and Se) is weakened. The atomic substitution also has an effect on the photophysical properties. From L-HKO to L-HKS, the emission peak at tautomer form red-shifts 70 nm. The energy gaps of the three compounds follow the decreased order of L-HKO (4.866 eV) > L-HKS (4.753 eV) > L-HKSe (4.371 eV) with the weakened electron-withdrawing ability of atom (from O to S and Se), which leads to the gradual red-shift of the absorption spectra from L-HKO to L-HKS and L-HKSe.