第一部份我們利用點擊反應合成出一系列以芘為橋連基團的雙芳杯化合物15，16和17，希望能夠利用芘的π-π堆疊作用力提高成膠的能力，並以化合物18作為對照。針對上述化合物作膠體測試後，發現化合物15能夠與二甲基甲醯胺、甲苯和對二甲苯形成凝膠，其中在二甲基甲醯胺裡有最低臨界膠體濃度1.0 w/v %─為一超級凝膠體。我們利用核磁共振光譜、紫外可見光及螢光光譜、紅外光光譜、掃描式電子顯微鏡、穿透式電子顯微鏡及共軛焦雷射掃描顯微鏡等作一系列的實驗量測或形貌的拍攝，綜合所得資料對此一化合物的成膠能力加以探討。
第二部分以芳杯為骨架的單態氧感測器為主題，此類化合物在文獻上鮮少報導，我們利用點擊反應在芳杯下緣修飾以蒽為架橋之芳杯化合物25，並以化合物23作為控制化合物。以365 nm和350 nm波長之光源激發進行環氧加成，並利用核磁共振光譜針對化合物的反應性與安定性進行研究。

In the first part, we have synthesized a series of pyrene-bridged biscalix[4]arenes 15, 16 and 17 by click reaction. We wish to increase the ability of forming gels via the π-π stacking interaction of the pyrene group. Compound 18 was used as a control compound. The biscalix[4]arene 15 was found to form gels in dimethylformamide, toluene, and p-xylene. The critical gelation concentration was found to be 1 w/v % in dimethylformamide, which meant it was a supergelator. To gain insight into the gelation properties of compound 15, we used NMR, IR, UV-Vis, fluorescence spectroscopy, SEM, TEM and Confocal Laser Scanning Microscopy to study the morphology of related gelation.
The subject of the second part of this Thesis was about the synthesis of a calix[4]aren-based singlet oxygen sensor. These type of compounds were rarely reported in the literature. Compound 25, with an anthracene-bridged calix[4]arene on its lower rim was synthesized by click reaction. Compound 23 was a control compound. UV light of 365 nm and 350 nm was used as irradiation source for the cyclooxidation. The reactivity and stability of the photooxidation products was monitored by NMR spectroscopy.

第一部分
以芘為橋連之雙芳杯系列衍生物的膠體性質研究
第一章 緒論 2
1.1 超分子化學簡介1 2
1.2 芳杯的簡介2 3
1.2.1 芳杯的簡史 3
1.2.2 芳杯的合成 5
1.2.3 雙芳杯之合成與應用 7
1.3 凝膠簡介 9
1.3.1 水凝膠(hydrogels) 10
1.3.2 氣凝膠 (aerogels) 11
1.3.3 有機凝膠(organogels) 12
1.4 具芳杯骨架之有機凝膠 13
1.5 具芘基之有機凝膠 16
1.6具1,2,3-三唑官能基之有機凝膠 19
第二章 研究動機 25
第三章 結果與討論 27
3.1 合成策略 27
3.2 丙炔基芳杯化合物2和3之製備31 27
3.3 二疊氮芘之合成 27
3.3.1 2,7-二疊氮芘4之製備 28
3.3.2 1,6-和1,8-二溴基芘6和7之合成 30
3.3.3 1,6-二疊氮芘9之合成 30
3.3.4 1,6-和1,8-二胺基芘10和11之合成 32
3.3.5 1,8-二疊氮芘12之合成 32
3.4 1,4-二疊氮苯14之合成42 33
3.5 雙芳杯單橋聯之系列衍生物的合成 33
3.6 雙芳杯化合物的1H NMR光譜鑑定 36
3.7 雙芳杯化合物的膠體測試 39
3.7.1 臨界膠體濃度與超級凝膠體(supergelators) 39
3.7.2 雙芳杯化合物的膠體測試結果 40
3.8 利用變濃度核磁共振氫譜來觀察化合物15的自組裝行為 43
3.9 利用變溫核磁共振氫譜觀察化合物15的自組裝行為 48
3.10 利用霍氏轉換紅外光譜探討自組裝行為 54
3.11利用紫外可見光譜及螢光放射光譜探討自組裝行為 57
3.12 利用掃描式電子顯微鏡(SEM)來觀察凝膠形貌。 59
3.13 利用穿透式電子顯微鏡(TEM)來觀察凝膠形貌。 61
3.13 利用共軛焦雷射掃描顯微鏡(CLSM)來觀察凝膠形貌。 64
第四章 結論 66
第二部分
芳杯下緣以蒽為橋連之環氧化加成反應研究
第一章 緒論 69
1.1 光化學簡史 69
1.2 蒽的光化學反應 71
1.3 單態氧的簡介 71
第二章 研究動機 75
第三章 結果與討論 77
3.1 合成策略 77
3.2 橋連基的合成 77
3.2.1 9,10-二氯甲基蒽19的製備68 77
3.2.1 9,10-二疊氮甲基蒽20的製備 78
3.3 丙炔基化合物的合成 78
3.3.1 4-第三丁基苯基丙炔基醚22的製備70 78
3.3.2 二丙炔基芳杯化合物3的製備 79
3.4 一價銅催化之1,3-偶極環化反應 79
3.4.1 控制化合物23的合成 79
3.4.2 芳杯化合物25的製備71 80
3.4.3 化合物25和26的鑑定 81
3.4.4 化合物25的核磁共振氫譜分析 84
3.5 控制化合物23與芳杯化合物25之紫外可見吸收光譜 86
3.6 控制化合物23的光照環氧加成反應 87
3.6.1 以氘二氯甲烷作為溶劑 88
3.6.2 以氘氯仿作為溶劑 91
3.6.2 大氣狀態，以波長 350 nm激發 93
3.7 芳杯化合物25的光照環氧加成反應 94
3.7.1 激發光源波長365 nm 95
3.7.2 激發光源波長350 nm 95
3.7.3 利用高解析質譜儀作探討 99
3.8 利用理論計算對芳杯化合物27反應性作探討 102
第四章 結論 104
實驗部分
1.1 實驗儀器及樣品製備方法 105
1.2 實驗藥品 108
1.3 合成步驟 109
參考文獻 125

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