Shining light on fluoride detection: a comprehensive study exploring the potential of coumarin precursors as selective turn-on fluorescent chemosensors

Abstract

In this study, we report a fluoride chemosensor based on the use of a non-fluorescent pre-coumarin, compound 1. This compound undergoes selective fluoride-triggered formation of coumarin 2, with a concomitant turn-on fluorescence signal. Although compound 1 exists as a mixture of alkene isomers (2 : 1 in favor of the E isomer), only the minor Z-isomer undergoes cyclization. Nonetheless, comprehensive computational and experimental studies provide evidence that in situ isomerization of E-1 to Z-1, followed by fluoride-triggered phenolate evolution and intramolecular cyclization, facilitates the generation of coumarin 2 in high yield. Moreover, this system is an effective turn-on fluorescence sensor for fluoride anions, which displays outstanding selectivity (limited response to other commonly occurring analytes), sensitivity (lowest reported limits of detection for this sensor class), and practicality (works in solution and on paper to generate both fluorometric and colorimetric responses). Ongoing efforts are focused on expanding this paradigm to other pre-coumarin scaffolds, which also undergo analyte-specific coumarin formation accompanied by turn-on fluorescence.