含雙異咢唑芳香取代雙芳杯衍生物之合成、性質探討與應用研究

Abstract

近年來，因雙芳杯結構上的特殊性，衍生出如變構效應、分子內震盪與分子構型轉換等有趣的性質，故雙芳杯衍生物的研究極受重視。本論文藉由炔類與雙腈氧基取代芳香環，進行雙重與四重的1,3-偶極環化加成反應，來建構雙芳杯分子系統。這一系列的雙芳杯分子有許多有趣的性質與應用，例如: 能辨識客體分子甲基紫精、開環化合物為阻轉異構物，與具有超分子膠性質。 修飾上蒽螢光基團的雙橋聯雙芳杯化合物26，能對甲基紫精進行辨識，結合常數為Ksv = 1377.6 M-1，雖然錯合常數較小，但優點是能利用螢光儀快速且簡便的進行偵測。雙橋聯雙芳杯26分子，所含的天然孔洞與陽離子-的作用力，是其能辨識甲基紫精的重要關鍵。此外，開環雙芳杯化合物28，因為蒽基團1,4,5,8-號位置上的氫，造成的立體障礙，限制其自由旋轉，而形成一組阻轉異構物。 於乙腈溶劑中，雙芳杯化合物24，會自組裝形成奈米粒子或微米球體，進一步組裝為藍色螢光超分子膠體。進一步針對超分子膠體進行應用研究，合成了雙芳杯化合物63，發現其能在油水混合溶劑中，相選擇性的膠化油層，期望此超分子膠體，未來能應用於原油外漏事件的處理。

In recent years, biscalix[4]arenes have been extensively studied because their structures usually contain interesting properties including the allosteric effect, intramolecular oscillation, and conformational interconversions. We have been using a strategy to construct a variety of functionalized isoxazoline and isoxazole unit(s) onto the calix[4]arene skeletons through double and/or quadruple 1,3-dipolar cycloaddition reactions of alkynes with aryl nitrile oxides. To our delight, these new series of biscalixarene derivatives contain various interesting properties, such as molecular recognition of methyl viologen, atropisomers of the ring-opened products, and supramolecular organogels. The biscalix[4]arene 26, with two parallel anthracene units, was found to show some affinity to as methyl viologen. Although the binding constant of biscalix[4]arene 26 with methyl viologen is small (137.47.6M1), it has the advantages of fast and easy screening by fluorescence spectroscopy. Cationic- interaction as well as a proper cavity size play key roles in the complexation of biscalix[4]arene 26 with methyl viologen. Moreover, biscalix[4]arenes 28a and 28b, were found to be atropisomers at room temperature. These two conformers were unable to exchange at room temperature owing to the restricted rotation of the C9C11 or C10C12 bonds of the -amino-,-unsaturated ketones of anthracene. We are suprised to find that biscalix[4]arene 24 capable of spontaneous self-assembly into nanoparticles and microspheres in CH3CN, and it eventually formed stable blue-light emitting supramolecular organogels. Follow the work, we synthesis the organogel 63, which can selectively gel the oil phase from an oil-water mixture. This gelator molecule holds future promise for oil spill recovery treatment.