Anthryl-1,2,4-oxadiazole-substituted calix[4]arenes as highly selective fluorescent chemodosimeters for Fe(3+).

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 Fe(3+) and Cu(2+) , whereas that of 2 was selectively quenched only by Fe(3+) . Control compound 4 was also selectively quenched by Fe(3+) , 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 Fe(3+) is also discussed. Furthermore, it should be noted that the oxadiazole-substituted anthracene 4 and calix[4]arene 2 are Fe(3+) -selective fluorescent chemodosimeters without the interference by Cu(2+) .