Synthesis of Anthryl Triazole Bridged Bispillar[5]arene and Biscalix[4]arene as Fluorogenic Sensors of Imidazolium Cations and Metal Ions

• Main Authors: Li, Hsin-Hung, 黎訓宏
• Other Authors: Chung, Wen-Sheng
• Format: Others
• Language: zh-TW
• Published: 2014
• Online Access: http://ndltd.ncl.edu.tw/handle/59558766668771970898

碩士 === 國立交通大學 === 應用化學系碩博士班 === 103 === 　　We have synthesized anthryl triazole bridged pillar[5]arene dimer as compound 40 which containing anthracene as a fluorophore by click reaction. Compound 40 was analyzed by UV-Vis absorption spectroscopy, fluorescence emission spectroscopy, ¬1H-NMR titration, ROESY and DOSY, which showed binding abilities toward different nitrogen-contained cations G1 to G5 and influence of varying substituted imidazolium G5 to G8. 　　UV-Vis spectra of compound 40 didn’t change when G1-G8 were added. However, the fluorescence intensity of compound 40 was enhanced when G1, G2, G3 and G5 were added. The binding ability of compound 40 calculated by Hill plot showed that it binds stonger toward G5 than G1 and G2. Imidazolium with different length of carbon chains and 2-methyl substituted were also studied. Binding constant obtained by Hill plot became larger as the length of alkyl chain being longer. Furthermore, the more hindered imidazolium G8 showed no fluorescence enhancement ability of compound 40 compared with G6 which have equal length of alkyl chain. As results, we believed the methyl group on 2-position played an important role which increased the steric hindrance and prevented it from threading into the cavity of pillar[5]arene 40. As NMR spectra showed, no signal shift of G8 while mixing with 40 compared with G6 which means no complex was formed. DOSY also indicated that G8 cannot form a complex with compound 40. NMR titration and Job plot showed 40 and G5 formed 1:2 complex. 2D-ROESY spectra indicating alkyl chain side of G5 were penetrated into the cavity of pillar[5]arene. DOSY also demonstrated that a new complex was formed. 　　According to the previous work of our laboratory, we have also synthesized biscalix[4]arene 44 using click reaction. The binding properties of host 44 toward 15 metal perchlorates were investigated by UV-Vis and fluorescence spectroscopy. The results showed that host 44 was highly selective toward Cu2+. Upon titration with Cu2+, the fluorescence of 44 was quenched (On-Off). Cu2+ was found to be reduced to Cu+ by host 44 according to the previous researchs in our laboratory.88