Substituent effect on ESIPT mechanisms and photophysical properties of HBT derivatives

Substituent effects on excited-state intramolecular proton transfer (ESIPT) and photophysical properties of 2-(2-Hydroxyphenyl) benzothiazole (HBT) derivatives have been theoretically unveiled via the density functional theory (DFT) and time-dependent DFT (TDDFT). The optimized geometrical configurations and normal mode analyses confirm that the proton transfer processes are more reactive in excited state. Through calculating the activation energies and rate constants of ESIPT processes, finding that the processes are increasingly inactive when substituent group changes from -CN, -CO₂Me, -Cl, -Me, -NMe₂ to -NO₂. In addition, the photophysical properties analyses indicate the vertical transition energies are in good agreement with those observed in experiment. Note that all the absorption and emission maxima of enol and keto forms have the significant red-shift. In order to clarify the substituent effect on ESIPT and photophysical properties, we draw the frontier molecular orbitals (FMOs) isosurfaces and calculate the distances of electrons and holes and atomic charges. It follows that the intramolecular charge transfer (ICT) degrees are increasingly enlarged as substituting from -CN, -CO₂Me, -Cl, -Me, -NMe₂ to -NO₂ groups, which not only causes the red-shift of absorption and emission of enol and keto forms, but also affects the charge distribution of proton donor and acceptor, inhibiting the occurrence of ESIPT processes.