American Chemical Society
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Upper Rim Allyl- and Arylazo-Coupled Calix[4]arenes as Highly Sensitive Chromogenic Sensors for Hg2+ Ion

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journal contribution
posted on 2005-04-15, 00:00 authored by Tsui-Lien Kao, Chiung-Chiu Wang, Yu-Ting Pan, Ya-Jiun Shiao, Jhy-Yuan Yen, Chun-Mei Shu, Gene-Hsiang Lee, Shie-Ming Peng, Wen-Sheng Chung
The syntheses and chromogenic properties of calix[4]arenes, carrying 5,17-bisallyl-11,23-bis(p-X-phenyl)azo 3ac, 5,11,17-triallyl-23-(p-X-phenyl)azo 4ac, and 5,17-bis(hydroxypropyl)-11,23-bis(p-X-phenyl)azo groups on the upper rims 5a,b, are described. Unexpectedly, UV/vis spectra of the very popular 4-(4-nitrophenyl)azophenol-coupled calix[4]arenes 3c and 4c did not show any shift in λmax when 10 different metal perchlorates were added separately to the host in a methanol−chloroform (v/v = 1/399) cosolvent. In contrast, the absorption spectra of calix[4]arenes with either 4-methoxyphenylazo (3b5b) or 4-phenylazo (3a5a) on the upper rim showed substantial bathochromic shifts (Δλ = 128−162 nm) upon the addition of soft metal ions (such as Hg2+, Cr3+, and Cu2+). The 4-(4-methoxyphenyl)azophenol-coupled calix[4]arenes (the 3b5b series) are found to be highly sensitive for mercury ion (Hg2+) among the 10 different metal ions screened. Strong interactions between Hg2+ ion and the 4-(4-methoxyphenyl)azophenol(s) as well as the p-allyl groups are corroborated by the 1H NMR studies of 3a,b·Hg2+ complexes. Furthermore, Job's plots revealed 1:1 binding stoichiometry for all these p-allyl- and arylazo-coupled calix[4]arenes with transition metal ions, and Benesi−Hilderbrand plots were used for the determination of their association constants.