Highly Selective and Sensitive Colorimetric and Fluorescent Chemosensors for Rapid Detection of Cyanide Anions in Aqueous Medium: Investigation on Supramolecular Recognition of Tweezer‑shaped Salophenes

Three tweezer‑shaped salophenes having catechols (1), phenols (2) and anisoles (3) units in conjunction to the dipodal Schiff bases have been applied for the optical sensing of cyanide (CN¯) ions in CH3CN-H2O (7:3) as solvent of choice. Among them, compounds 1 and 2 recognized CN¯, relying on distinct color and spectral changes. They are easy-to-use probes that exhibit extremely high sensitivity (limit of detection = 1–10 nM), rapid response (5 s) and excellent selectivity. Moreover, the visual detection and concentration determination of CN¯ by solution test kits of both sensors are the advantages for the practical applications. Based on the fluorescence and NMR spectroscopy, as well as the OH¯ and reversibility experiments, the explicit effect of hydroxyl groups on sensing and as well the different recognition of 1 and 2 toward CN¯ ions was proved. While probe 1 senses CN¯ via deprotonation, probe 2 recognizes it through an intramolecular aldimine condensation cyclization, leading to formation of anions of dihydroxyquinoxaline 4. This chemodosimetry is being reported for the first time in a Schiff’s base. Furthermore, the similarity of fluorescence and NMR responses of 2 and 4 toward CN¯ supports the proposed process.