Anthryl-1,2,4-oxadiazole-Substituted Calix[4]arenes as Highly Selective Fluorescent Chemodosimeters for Fe3+

Abstract

Fluorescent chemosensors 1 and 2, with 1,2,4-oxadiazoles as the binding ligands and anthracene as the fluorophore, were synthesized through sequential 1,3-dipolar cycloaddition reactions of 25,27-dioxyacetonitrilecalix[4]arenes 8 and 11. The fluorescence of 1 was severely quenched by both Fe3+ and Cu2+, whereas that of 2 was selectively quenched only by Fe3+. Control compound 4 was also selectively quenched by Fe3+, which implied the importance of anthryl-1,2,4-oxadiazole core; furthermore, it was shown to give various oxidation products such as oxanthrone 13, anthraquinone 14, and imidazolyl oxanthrone 15. In addition to product separation and identification, the fluorescent quenching mechanism of these 9-anthryl-1,2,4-oxadiazolyl derivatives by Fe3+ is also discussed. Furthermore, it should be noted that the oxadiazole-substituted anthracene 4 and calix[4]arene 2 are Fe3+-selective fluorescent chemodosimeters without the interference by Cu2+.