1,4-雙三唑二苯乙烯為橋聯之雙芳杯衍生物之合成、膠體性質與自組裝研究

Abstract

本論文主要探討芳杯上三級辛基形成之凡得瓦作用力、及橋聯基團改為二苯乙烯對於形成膠體所造成的影響。我們成功利用點擊化學反應及1,3-偶極環化反應，合成出化合物47、48及49。經過一系列膠體性質測試，我們發現芳杯上緣為三級辛基的芳杯對於形成膠體之能力並沒有提升。且對照實驗室合成之化合物甚至出現更不好的現象，我們推測此現象的產生可能是三級辛基的立體阻礙過大，導致有機溶液無法進入芳杯的孔洞，故降低此類雙芳杯形成凝膠的能力。 含有偶氮苯之雙芳杯化合物49可經照光得到順式，而順式偶氮苯可藉由照光及溫度調控回復到反式之特性。目前已有許多文獻討論影響順反異構化速率之因素，在本文中主要以一系列偶氮苯為橋聯之巨環分子 (Macrocycles) 進行可能機制之探討。由芳杯上緣無取代基之化合物53、三級丁基之化合物51及三級辛基之化合物49，我們可以發現，其活化能隨著芳杯分子量增加而有些微上升之趨勢，因此我們認為rotation扮演重要機制，但此推測乃有討論空間，需借助更多對照化合物及理論計算以利釐清反應機制。 另一方面，我們也將原本為偶氮苯之橋聯基團改為等量 (isosteric) 化合物二苯乙烯及在二苯乙烯鄰位接有磺酸之官能基團利用點擊化學反應成功合成出化合物62、63。化合物62與63會在特定有機溶劑下形成膠體，且化合物62在加入己烷時會有立即產生膠體之現象。藉由掃描式與穿透式電子顯微鏡來探討其自組裝的形貌，並運用變溫NMR、紫外-可見光吸收光譜、紅外光譜儀來推測自組裝的模型。

In this thesis, we replaced t-butyl group with t-octyl group to synthesize compounds 47, 48, and 49. Also we synthesized stilbene bridged biscalix[4]arene 62, and 63 to study their gel properties. According to the results, we found compounds 47, 48, and 49 did not show any gel property in 21 organic solvents. The results imply that t-octyl group maybe too bulky that the organic solvent can not enter the cone of the compound. Interestingly,compound 62 does form gels in hexanes, ethanol, IPA, n-propanol while compound 63 could form gel only in EA. We also noticed that the compound 62 can form gel immediately in hexanes. Variable-temperature 1H-NMR, and uv-vis spectra, SEM, TEM, and IR spectroscopy were used to gain our understanding of possible packing model of compound 62. Furthermore, we study the thermally induced cis-trans isomerization of a series of azobenzene-bridged macrocycles. According to the literatures, two mechanisms—rotation and inversion, have been proposed as possible pathways for azobenzene thermal isomerization. We observed that the activation energies of cis to trans isomerization of azobenzene increased as the weight of substitutes in the calixarene increased. It meant that the rotation mechanism be playing a important role. The mechanisms of these azobenzene-bridged macrocycles still remain to be discussed further, and the computational calculations is worthy of studying.