A specific and ratiometric chemosensor for Hg(2+) based on triazole coupled ortho-methoxyphenylazocalix[4]arene

Abstract

Calix[4]arene 3, which contains two distal triazole groups on the lower rim and two distal o-methoxyphenylazo groups on the upper rim, was synthesized and found to be a specific and ratiometric sensor for Hg(2+) in a polar protic solvent. A series of o-methoxyphenylazo derivatives (3, 4, 5, 7, and 9) were synthesized, which proved that the lower-rim triazoles and the hydroxyl azophenol(s) were the major ligands for metal ion binding. Though analogues 4 and 10 showed some sensitivity for Hg(2+), compound 3 was the only ratiometric chemosensor for Hg(2+) among the series of azocalix[4]arenes synthesized in this work. The formation of 3. Hg(2+) complex was supported by UV/vis and NMR titration studies and Mass spectrometry. Based on the symmetrical features of NMR spectra of 3 center dot Hg(2+), the complex is believed to be symmetrical with respect to the calix[4]arene cavity. Furthermore, the complex was determined to be 1:1 binding stoichiometry by Job's plot, and the association constant was determined to be 4.02 x 10(3) M(-1) using Benesi-Hildebrand plot. (C) 2011 Elsevier Ltd. All rights reserved.