臺灣博碩士論文加值系統

本論文研究芴酮(Fluorenone)的衍生物和Fluoren-9-Ylidene Malononireile 衍生物，並用紫外可見光譜儀、螢光光譜儀來探討在不同性質溶劑下光物理特性。我們設計合成四種新的螢光分子，以Fluorene為骨架，分別在9號碳導入電子親核力強的基團(Cyano)、及酮基(CO group)，以及在3,6號碳分別導入 Ethynyl-pyridine 基團。我們從結構、分子取代基、溶劑效應之不同角度來探討所影響的UV-Vis吸收和發射（熒光）帶的位置、強度和形狀的變化。而在檢測溶劑方面，我們分為極性和非極性溶劑及質子及非質子溶劑，同時也計算了螢光量子產率(quantumyield)。對於合成之中間物以及最後產物可以藉由核磁共振光譜(NMR)、質譜儀(Mass)、IR等光譜鑑定其官能基的變化以及結構的形成。

The synthesis of four fluorene-based compounds when Fluorenone (CO) and Fluoren-9-Ylidene Malononireile C(CN)2 derivatives were introduced into position 9 of molecule by reported. The structures of Fluorenone (CO) and Fluoren-9-Ylidene Malononireile C(CN)2 derivatives were confirmed Mass spectrometry, FT-IR and NMR. The optical properties were analyzed by Absorption and fluorescence properties of compounds in polar solvents and observed solvatochromic behavior. Subsequently the fluorescence quantum yield of compounds was calculated.Then showing that higher values were obtained for compounds when CO derivative was present in molecule.

摘要 i
ABSTRACT ii
誌謝 iii
目錄 iv
表目錄 vii
圖目錄 viii
附圖目錄 xi
第一章 緒論 1
1.1 前言 1
1.2 理論 2
1.2.1 螢光發光的原理 2
1.2.2 紫外光可見光光譜 3
1.2.3 溶劑效應 3
1.2.4 溶劑效應影響吸收光譜 4
1.2.5 溶劑效應影響螢光放射光譜 5
1.2.6 濃度對螢光強度的效應 6
1.2.7 螢光量子產率的計算 7
1.2.8 影響螢光的因素 8
第二章 文獻回顧 10
2.1 Ambipolar Fluoren-9-Ylidene Malononitrile 的衍生物之光物理性質 10
2.2 Cyanine系列的Fluorene衍生物應用在DNA的偵測 12
2.3 Sonogashira反應的起源與發展 15
2.4 Poly( fluorine) 應用在發光二極體 20
2.5 9-Fluorenone應用在感光劑 21
第三章 研究動機 24
3.1 研究動機與目的 24
3.2 分子設計 25
第四章 實驗 28
4.1 實驗儀器 28
4.2 實驗室藥品 29
4.3 產物合成 30
3,6-Dibromo-phenanthrene-9,10-dione (2) 之製備 30
3,6-Dibromo-fluoren-9-one (3) 之製備 30
3,6-Bis-pyridin-2-ylethynyl-fluoren-9-one (1a) 之製備 31
2-(3,6-Bis-pyridin-2-ylethynyl-fluoren-9-ylidene)-malononitrile (2a) 之製備 32
3,6-Bis-pyridin-3-ylethynyl-fluoren-9-one (1b) 之製備 32
2-(3,6-Bis-pyridin-3-ylethynyl-fluoren-9-ylidene)-malononitrile (2b) 之製備 33
4.4 光學性質測試 34
紫外光-可見光光譜儀 34
螢光量子產率 34
第五章 結果與討論 36
5.1 分子鑑定 36
5.2 產物之光學分析 41
5.2.1產物溶解於acetonitrile之光學分析 41
5.2.2產物溶解於DMSO:H2O=1:9之光學分析 43
5.2.3螢光量子產率分析 45
5.2.4 在非質子溶劑下的溶劑顯色效應 45
5.2.5在質子溶劑下的溶劑顯色效應 47
5.2.6產物溶解於不同水的比例之螢光光學分析 49
第六章 結論 52
參考文獻 53
附圖 56

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