Chemosensors for Metal Cations and Anions Based on Calix[4]arene with Lower-Rim Triazoles

• Main Authors: Wang, Nae-Jen, 王乃珍
• Other Authors: Chung, Wen-Sheng
• Format: Others
• Language: zh-TW
• Published: 2012
• Online Access: http://ndltd.ncl.edu.tw/handle/3j8fza

博士 === 國立交通大學 === 應用化學系碩博士班 === 101 === In this thesis, chromogenic and fluorogenic calix[4]arenes bearing lower-rim triazoles as chemosensors for metal cations in polar protic cosolvents were synthesized and studied. Besides, the lower-rim distal triazoles of calix[4]arene as an anionic recognition site and chromogenic group were also explored. In chapter 2, a specific and ratiometric chemosensor for Hg2+ based on triazole coupled ortho-methoxyphenylazocalix[4]arene 4 was synthesized. The complex 4?杳g2+ was determined to be 1:1 stoichometry and its association constant was determined to be 1.07(?b0.32) ?e 104 M-1 in a MeOH/CHCl3 (v/v, 98:2) cosolvent. The functions of azo, hydroxyl, and triazole groups on ligand 4 for sensing Hg2+ were distinguished by the studies of ligands 4 and its derivatives. In chapter 3, a novel fluoroionophore, triazolylpyrene, was developed. Furthermore, a calix[4]arene with lower-rim proximal triazolylpyrenes 18 is a ratiometric fluorescent chemosensor for Ag+ with higher sensitivity compared to that of a calix[4]arene with lower-rim distal triazolylpyrenes 20, and the conventional fluoroionophore with “triazole-CH2-pyrene”. In a MeOH/CHCl3 (v/v, 98:2) cosolvent, the complex 20?服g+ was determined to be 1:1 stoichometry and its association constant was determined to be 1.83(?b0.33) ?e 104 M-1; however, the complex 18?服g+ was determined to be 1:1 stoichometry and its association constant was determined to be 7.11(?b0.80) ?e 103 M-1. Even the detection of Ag+ by ligand 18 works in 10% aqueous methanol solution. In chapter 4, calix[4]arenes bearing lower-rim distal p-substituted phenyltriazoles were developed where the electronegativity of triazoles are controlled by its conjugated p-substituted benzene. Especially, a calix[4]arene with lower-rim distal p-nitrophenyltriazoles 30 was explored to be a novel ratiometric and chromogenic chemosensor toward F?{, CH3COO?{, H2PO4?{, and HO?{ in polar solvent as well as in polar protic cosolvents.