A ratiometric fluorescent probe for fluoride ion employing the excited-state intramolecular proton transfer

Abstract

A ratiometric fluorescent probe 1 for fluoride ion was developed based on modulation of the excited-state intramolecular proton transfer (ESIPT) process of 2-(2′-hydroxyphenyl)benzimidazole (HPBI) through the hydroxyl group protection/deprotection reaction. The probe 1 was readily prepared by the reaction of HPBI with tert-butyldimethylsilyl chloride (TBS-Cl) and shows only fluorescence emission maximum at 360 nm. Upon treatment with fluoride in aqueous DMF solution, the TBS protective group of probe 1 was removed readily and ESIPT of the probe was switched on, which resulted in a decrease of the emission band at 360 nm and an increase of a new fluorescence peak around 454 nm. The fluorescent intensity ratio at 454 and 360 nm ( I 454/ I 360) increases linearly with fluoride ion concentration in the range 0.3–8.0 μmol L −1 and the detection limit is 0.19 μmol L −1. The proposed probe shows excellent selectivity toward fluoride ion over other common anions. The method has been successfully applied to the fluoride determination in toothpaste and tap water samples.