含芘三唑取代之苯醌芳杯及其衍生物之離子感測研究

Abstract

在本研究中利用點擊化學修飾芳杯下緣，引入芘為螢光發射基團，並延續實驗室陳映蓉學姐的意外發現，利用過量的過氯酸鐵，有效合成出苯醌芳杯之骨架，衍生出更加多樣性的分子。故在本研究中，合成下緣為芘三唑取代的苯醌芳杯之衍生化合物3336。由實驗結果，我們發現化合物33，因其骨架改變，使其螢光放射強度減弱，進而影響其光學性質；化合物34對Zn2+與Cd2+離子有單體激態雙體的螢光變化；化合物35原本預期可以做為雙調控的離子感測器，因其合成上的困難，因此沒有後續的感測探討；化合物36對於Ca2+與Pb2+離子有較明顯的選擇性，錯合前後可造成顏色的變化；另外，化合物36加入陰離子如F-、AcO-及H2PO4-，亦可以由肉眼觀察其顏色變化。此外，我們更進一步利用氫核磁共振光譜探討化合物34與化合物36之離子錯合模型，並相互印證比較其差異。

In this study, we modified the lowerrim of the calix[4]arene by attaching distal pyrene unit as the fluorophore through the click chemistry of pyrene azides with 25, 27bispropargyl calix[4]arene. Based on the methods developed by Ms. YingJung Chen, we successfully synthesized the unique skeleton of calix[4]quinone and its derivatives 3336. Based on the results from UVVis spectroscopy and fluorescence spectrometry, we found that fluorescence emission intensity decreased, because more flexible structure will cause energy lost in the cases of 33; 34 possesses an efficient excimer formation and emission, and the fluorescent spectra changes observed upon addition of various metal ions show that 34 is selective for Cd2+ and Zn2+ over other metal ions; Owing to the low yield of 35, we didn’t investigate the allosteric effect of 35. In addition, compound 36 was found to change color when anion such as F-, AcO- and H2PO4- was added to its solution. Moreover, we further investigate the complexation models by using NMR titration spectroscopy.