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| 研究生： |
李佩倫 Lee, Pei-Lun |
|---|---|
| 論文名稱： |
在空間中具低對稱性之六環螺旋烴:合成研究､結構分析及其性質探究 Hexapole Helicenes with Low Symmetry in Three-Dimensional Geometry:Syntheses, Structural Analyses and Properties |
| 指導教授： |
吳耀庭
Wu, Yao-Ting |
| 學位類別： |
碩士 Master |
| 系所名稱： |
理學院 - 化學系 Department of Chemistry |
| 論文出版年： | 2021 |
| 畢業學年度： | 109 |
| 語文別： | 中文 |
| 論文頁數： | 141 |
| 中文關鍵詞： | 多環螺旋烴 、[6]螺旋烴 、[7]螺旋烴 、三亞苯 |
| 外文關鍵詞： | multiple helicenes, [6]helicenes , [7]helicenes, triphenylene |
| 相關次數： | 點閱：164 下載：0 |
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多環螺旋烴 (multiple helicenes)，是一種由多個單一螺旋烴結構藉由鄰位所稠合而成的多環芳香烴結構，和單螺旋烴相比，由於其高度扭曲的結構，於近年來成為一個快速成長的研究主題，更因為其特殊的光物理性質，使得多環螺旋烴在圓偏振發光等有機發光材料能被運用。
本論文以三亞苯為中心結構進行了多環[6]螺旋烴的合成，也進行了 π 共軛系統之延伸，合成出多環[7]螺旋烴。在合成路徑的設計上，本論文以三碘化合物40a、40b、53a、53b為前驅物，透過碳-氫鍵活化環加成反應成功合成出六環[6]/[4]螺旋烴化合物:43a、43b、44a、44b，六環[7]/[4]螺旋烴化合物:56a、六環[6]/[5]螺旋烴化合物:58及九環[6]/[5]/[4]螺旋烴化合物:59。但是在嘗試合成六環[6]/[5]螺旋烴化合物:70時，因為其三碘化合物67前驅物之立體障礙因素無法順利進行合成，所以無法進行化合物70的合成。此外，本論文亦透過X-ray單晶繞射進行化合物43b的結構分析，發現化合物43b並非對稱結構，而是呈現C1的構型，此一結果與其類似的研究文獻所得到之構型皆不相同; 更藉由芳香性的分析發現在化合物43b中，越靠近其中心三亞苯的苯環其芳香性越弱。在未來的發展上，可嘗試利用三碘化合物前驅物進行官能基修飾以進行不同的 π共軛系統之延伸。
Multiple helicene, which is one kind of polycyclic hydrocarbons (PAHs) that is formed by multi-ortho-fused helicenes. Compared with single helicene, multiple helicene, because of its highly distorted structure which cause its special photo-physical properties has been applied to circularly photo-luminescent (CPL) materials in recent years. The thesis uses triphenylene as core structure to synthesize multiple[6]helicenes, furthermore, multiple [7]helicenes were even synthesized through π-system conjugations. The synthetic routes of muliple[6]helicenes and multiple[7]helicenes are synthesized by C-H bond activated annulation of triiodo group precursors of 40a、40b、53a、53b, obtaining four kinds of multiple helicenes: hexapole[6]/[4] helicenes: 43a、43b、44a、44b, hexapole [7]/[4] helicene: 56, hexapole[6]/[5] helicenes: 58, and nonapole [6]/[5]/[4] helicenes:59. The structure analysis of hexapole[6]/[4] helicene:43b was conducted by X-ray crystallography. From its crystal data, one can find out that 43b is not a symmetric structure, but the conformation of C1 point group, which is totally different from prior studies; besides, by the calculation of HOMA values, one can even find out that in 43b, the benzene rings which are closer to 43b core structure of triphenylene are much less aromatic. In future stud ies, one may try to conduct modification of triiodo functional group to make another π-system conjugated mutiiple helicenes.
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2026-08-20公開