The Synthesis of Calix[4]arenes with (1) Distal Anthryl-triazoles and Acid Derivatives (2) Distal Bis-Pyrenyl-ester-triazoles for Metal Ion Sensing Studies.

• Main Authors: Wang, Yu-Yun, 王雨筠
• Other Authors: Chung, Wen-Sheng
• Format: Others
• Language: zh-TW
• Published: 2009
• Online Access: http://ndltd.ncl.edu.tw/handle/18427518349799494126

碩士 === 國立交通大學 === 應用化學系所 === 97 === (1) The Synthesis of calix[4]arenes with Distal Anthryl-triazoles and Acid Derivatives for Metal ion Sensing Studies. We used the Click Chemistry to modify the lower rim of calix[4]arenes with a triazole cationic binding site, and an anthracene as a fluorophore. After we incorporating a second acid derivatives group into 5a, compounds 6a�{9a were obtained as fluoroionophores for metal ions. Compounds 5a�{9a and control compound 10a showed fluorescence quenching toward Cu2+, Hg2+, and Cr3+ ions. Besides that, 6a also showed a slight fluorescence quenching toward Pb2+ and Mn2+ ions; 8a showed fluorescence enhancement toward Ba2+, Ca2+, Cd2+, Li+, Mg2+, Pb2+ and Zn2+ ions; 9a showed fluorescence enhancement toward Ag+ and Cd2+. We inferred that the functional groups (amide and thioamide) of 8a and 9a might donate electrons to the anthryl group via PET mechanism, thus the fluorescence of anthryl group was quenched. When the functional groups of 8a and 9a bind with metal ions, the metal ions may inhibit the PET mechanism, and therefore enhance the fluorescence. Possible binding modes of these metal complexes were proposed based on 1H NMR titration experiments. (2) The Synthesis of calix[4]arenes with Distal Pyrenyl-ester-triazoles for Metal ion Sensing Studies. The lower-rim of calix[4]arenes was modified with triazoles as the cationic binding sites, and pyrenes as the fluorophores. Mono-substituted compound 15, bis-substituted compound 16, phenol protected compound 18 and control compound 14 were synthesized. Both 14 and 15 showed fluorescence quenching toward Cu2+, Hg2+ and Cr3+ ions. 16 showed both monomer and excimer fluorescence quenching toward Cu2+and Cr3+, but showed monomer enhancement and excimer quenching toward Hg2+. Compound 18 showed monomer enhancement and excimer quenching toward Ag+ and Zn2+ besides Cu2+, Hg2+ and Cr3+ ions. Note that the complex of 18˙Cu2+ formed a static excimer. We used 1H NMR titration experiment to determine possible binding modes of these metal complexes and proved that the hydroxyl group of 16 proceeded oxidation-reduction with Cu2+.