Manipulation of excited-state intramolecular proton transfer by electron-donor substitution for high performance fluoride ions sensing

Abstract

Excited-state intramolecular proton transfer (ESIPT) molecules has been using as a variety of functionalityled molecular systems. To investigate the relationship between the electron-donor substitution and luminescent properties of ESIPT luminogens, four 2-(2-hydroxyphenyl) benzothiazole derivatives with donor-π-acceptor (D-π-A)-structured were synthesized. The distinct fluorescence properties of them were found to be highly dependent on the electron-donor moiety (triphenylamine and anthracenyl), its substituent position (para and meta position) and solvent polarity. The M−TPA, P-En, and M−En showed ESIPT emission in organic solvents, while the P-TPA showed intramolecular charge transfer process (ICT) emission. It is due to the synergistic effect of the aggregation-induced emission (AIE) and ESIPT, that M−TPA and M−En exhibited high solid-state quantum yields and large Stokes shifts. They were used as a probe for detecting F−, which resulted in rapid colorimetric, high sensitivity and good selectivity. The M−TPA was a turn-on fluorescent probe, which had the best detection property, and the limit of detection was as low as 11 nM. Because M−TPA displayed phenol anion emission in DMSO and F− causes the deprotonation of the M−TPA, which led to significant red shift of the absorption band and enhancement of fluorescence emission. This work provides a reliable strategy for designing high-performance fluorescent sensor via ESIPT manipulation.