Unveiling the sensing mechanism and luminescence property of a new ESIPT-based fluorescent sensor for detecting Zn.

Recently, based on the mechanism of excited-state intramolecular proton transfer (ESIPT), a new fluorescent probe named 3-(benzo[d]thiazol-2-yl)-5-bromosalicylaldehyde-N-phenyl thiosemicarbazone (BTT) was successfully synthesized [Analyst 146 (2021) 4348-4356.]. However, the importance of ESIPT processes of BTT probe and the mechanism of detecting Zn ions have not been studied in detail. In this study, the photochemical behavior of ESIPT-chromophore and the photophysical changes of detecting Zn ions were explained at the molecular level for the first time. The calculated spectral values were in agreement with the experiment. We not only confirmed the excited state hydrogen-bond strengthening by interaction region indicator (IRI), but also scanned the potential energy curves of BTT molecule in different electronic states, which confirmed that the hydrogen proton is easier to transfer in the first excited state. In addition, we had given the reasonable structure of the BTT-Zn complex (L1) by comparing the binding free energies. The hole-electron distribution and interfragment charge transfer (IFCT) methods proved the excitation type of intraligand charge transfer (ILCT). Finally, the photophysical phenomenon of BTT for detecting Zn ions is explained by calculating the electronic spectra and the energy gap (E) between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO).