2,3位置含長鏈吡啶二醯胺基團之蒽衍生物：碳橋基及碳鏈長度對於有機凝膠形成及固態刺激響應性質之研究

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姓名

饒旂華(Chi-Hua Jao) 查詢紙本館藏

畢業系所

化學學系

論文名稱

2,3位置含長鏈吡啶二醯胺基團之蒽衍生物：碳橋基及碳鏈長度對於有機凝膠形成及固態刺激響應性質之研究
(Anthracene Derivatives with Long-Chain Pyridyldicarboxamide Groups at 2,3 Positions: Investigation of Carbon Bridge and Chain Length Effect on Gel Formation and Solid State Stimuli-Responsive)

相關論文

★ 含有醯胺基團之乙炔蒽衍生物：碳氫長鏈與碳氟長鏈對於有機凝膠之形成及固態刺激響應行為之研究	★ 含有醯胺基團之乙炔蒽衍生物：取代基團位置對於有機凝膠之形成及固態刺激響應行為之研究
★ 含醯胺官能基之蒽衍生物及其刺激響應行為之研究

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至系統瀏覽論文 (2025-8-31以後開放)

摘要(中)

本篇論文合成出四個含有醯胺基團的雙取代蒽衍伸物，探討凝膠片段末端碳氫鏈長度，以及蒽主體與凝膠片段之間有無乙炔基連接，對於形成凝膠的能力及固態刺激響應行為之間的差異。從凝膠測試結果來看，此四種化合物皆可在多種有機溶劑中形成凝膠。經由變溫1H NMR去探討形成凝膠的作用機制，推測可能是透過分子間醯胺基團氫鍵以及芳香族環間之π-π作用力進行自組裝排列。此外，分別透過變溫吸收光譜、放射光譜及改變濃度的吸收、放射及激發光譜，探討分子間聚集的作用力關係對於光物理性質的影響，推測四個分子皆形成H-type aggregation的堆疊模式，且透過凝膠以及薄膜的光譜探討，可以推測分子間堆疊的程度。溶液態分子會隨著環境中水含量的提升，而觀察到明顯地放光強度增加以及光色的改變，即典型的AIEE特性。利用SEM能觀察到微觀尺度下，分子間聚集後所形成的不同形貌，發現凝膠分子會依據分子間作用的程度，出現以纖維狀相互纏繞或針狀結構聚集。透過PXRD探討置備乾凝膠後，分子間的堆疊模式，發現分子間聚集排列較不有序，而觀察到非晶性的中間相結果。最後也研究了四種化合物的固態粉末刺激響應行為的差異及特性，在機械力刺激下觀察到固態放光顏色的改變，且可透過溶劑蒸熏的方式使放光顏色回復，並可重複數個循環。

摘要(英)

In this thesis, we synthesized four anthracene-based disubstituted organogelators, FH76, FH146, FH158 and FH156. We made some structural modifications between these four compound, trying to figure out the different properties among them, including geling ability and solid state stimuli-response. We used anthracene as a core linked by gel segment at 2,3-position with different chain length by either ethynyl or single bond. From the gel test results, all four compounds formed organogels in various organic solvents. A variety of spectroscopic methods were employed to identify the driving forces responsive for gel formation and explored the photo-physical properties. It is speculated that the self-assembly arrangement occurs through intermolecular hydrogen bonding and π-π interaction. The stacking behavior suggests that all four molecules self-assemble through the H-type aggregation. It shows the typical AIEE property when gradually increase the water content in the THF solution, displaying the fluorescence intensity enhancement as well as color change. Different morphologies formed by intermolecular aggregation at the microscopic scale can be observed by SEM, and it is found that the gel molecules are entangled with each other in a fibrous form and aggregated in a needle-like structure. Also the intermolecular stacking patterns after preparing the xerogel were investigated by PXRD, and the mesophase results have seen which may come from the irregular stacking. Finally, the differences and characteristics of the solid state stimuli-response behavior of the four compounds were also investigated. It shows emissive color change upon grinding, and recover to the original emission when solvent fuming. The result is reversible and which can be repeated multiple cycles.

關鍵字(中)

★ 有機凝膠分子
★ 超分子自組裝
★ 蒽
★ 醯胺
★ 固態刺激響應行為材料

關鍵字(英)

★ Organogels
★ supramolecular self-assembly
★ anthracene
★ amide
★ solid-state stimuli-responsive behavior

論文目次

摘要 I
Abstract II
誌謝辭 III
目錄… IV
圖目錄 VII
表目錄 XV
化合物對照表 XVI
一、緒論 1
1.1前言 1
1.1.1凝膠的定義 2
1.1.2凝膠的形成 2
1.1.3凝膠的分類 3
1.2有機凝膠的分類 4
1.2.1含有蒽的有機凝膠 4
1.2.2含有醯胺官能基的有機凝膠 9
1.2.3含有芳香環的有機凝膠 13
1.2.4 雙取代的有機凝膠 17
1.3刺激響應 21
1.3.1具有刺激響應行為的分子 21
1.4分子堆疊模式 27
1.5研究動機 29
二、結果與討論 33
2.1合成與結構鑑定 33
2.2凝膠分子FL74、FL146、FL158、FL156之光物理性質 40
2.3凝膠分子的自組裝行為 47
2.3.1不同溶劑中形成凝膠能力的測試 47
2.3.2變溫核磁共振實驗 53
2.3.3變溫UV-Vis吸收實驗、變溫放光實驗 60
2.3.4變濃度UV-Vis吸收實驗、放射與激發光譜實驗 67
2.3.5稀薄溶液、凝膠、薄膜狀態的吸收及放射實驗 79
2.3.6分子聚集誘導放射強度增強的探討 88
2.3.6分子聚集形貌研究 98
2.3.7 FL74與實驗室近年所開發之凝膠分子比較 115
2.4 固態行為研究 117
2.4.1 Xerogel堆疊模式探討 117
2.4.2 刺激響應行為測試 122
2.4.3 熱穩定性質及熱刺激響應行為 125
三、結論 129
四、實驗部分 130
4.1 分析儀器 130
4.2 實驗藥品 134
4.3 實驗合成步驟 135
五、參考資料 152
六、附錄 159

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指導教授

孫世勝陳銘洲(Shih-sheng Sun Ming-Chou Chen)

審核日期

2022-10-20

推文