具C3對稱三聚茆之衍生物的合成、性質及其在超分子化學上的應用

Abstract

在本論文中，利用實驗室已發展出以三聚茚為主體C3對稱的立體骨架，即藉由在三聚茚C5、C10、C15號位置上修飾上苯環取代基創造出三維的架構中間體，用其獨特三維結構應用於超分子化學中。 第一部分合成有機凝膠分子TDMDA。利用在中間體上修飾具氫鍵作用力官能基及長碳鏈，發現在疏水性溶劑環己烷中可形成網狀結構的膠體，而在親水性甲醇溶劑中則形成奈米球微結構。同時我們藉由改變外自組裝外在環境，可在基板上直接轉換微結構。第二部分為分子辨識受體；係利用速配化學在中間體帶上具有π共軛苯環（TPTB、TDMTB）和芘的芳香環（TPTHP、TDMTHP）。利用1,2,3-三唑分子與鹵素離子間C-H…X-氫鍵作用力作為鹵素接受器，其中以氯的親和力最好。另外，藉由予體—受體的分子作用力，設計出與碳六十有良好作用力的受體分子。最後利用1H NMR及UV-Vis光譜滴定實驗證實。

In our previous studies, we developed an unique 3D skeleton based on truxene moiety. With incorporating various functional structures onto C5, C10, and C15 position of the truxene core, the successful synthetical strategy giving intriguing molecules through orthogonally and distinguishably modify active sites provides us an efficient way to further inspect on the diversity of its 3D derivatives. As a result, via involving the 3D truxene core, the thesis extend the applications of these various derivatives in supramolecular chemistry. Herein, we synthesized newly 3D organic gelator TDMDA which constructed by amide groups with long hydrocarbon chains. The morphology of TDMDA was found in fibrillar and globular morphology when dissolved in cyclohexane and methanol respectively and are characterized by SEM and TEM for close view. Moreover, gelator TDMDA incorporating amphipathic groups whose self-assembly display in-situ reversible transformation of aggregate morphology between fibrillar and globular upon exposure to different solvent. On the other hand, we also develope halide anion receptors TPTB and TDMTB from click chemistry. Accroding to NMR titration experiment, we found both of them have the best affinity to chloride due to the proper size of inner cavity. At last, we functionalized pyrene moiety onto the 3D architecture to achieve TPTHP and TDMTHP as C60 receptors, expecting it has good affinity with C60 via donor-acceptor and π-π interaction.