Atomic electronegativity-dependent intramolecular hydrogen bond and fluorescence characteristics of novel scaffold-based fluorophore: a TD-DFT study.

In this work, fluorescent properties and excited-state intramolecular proton transfer (ESIPT) processes of 2,5-bis(benzo[d]thiazol-2-yl)phenol (BTP) and its derivatives (BOP and BSeP) with different heteroatom atoms (O and Se) have been systematically explored by the density functional theory (DFT) and time-dependent DFT (TD-DFT) methods. The calculated absorption and fluorescence emission peaks agree well with the experimental values in acetonitrile. From the data of structures, topological parameters, reduced density gradient analyses, and infrared (IR) vibrational frequencies, the intramolecular hydrogen bonds (IHBs) of BTP and its derivatives are enhanced upon light-excitation. The potential energy curves show that the ESIPT process occurs in BTP and its derivatives after surmounting 0.167-0.306 eV energy barrier. The strength of intramolecular hydrogen bond, HOMO-LUMO energy gap, and red-shifted value of absorption and fluorescence emission wavelengths are dependent on the electron-withdrawing ability of heteroatom from O to S and Se. We believe that this work can pave the way for developing a new ESIPT-based fluorophore with better luminescent properties.