博碩士論文 103324029 詳細資訊




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姓名 劉冠廷(Kuan-Ting Liu)  查詢紙本館藏   畢業系所 化學工程與材料工程學系
論文名稱 鈀催化之碳氫鍵活化反應: 發展省步驟且具位向選擇性新合成途徑 快速製備有機光電材料重要之π-A-π結構
(Direct C-H Arylation as Rapid and Regioselective Access to Organic-Electronics-Versatile π-A-π Type Building Blocks)
檔案 [Endnote RIS 格式]    [Bibtex 格式]    至系統瀏覽論文 (2018-8-1以後開放)
摘要(中) 無論是在小分子與高分子有機光電材料中,在拉電子基團 (Acceptor) 兩側嵌上不同的官能基團所合成的π-A-π結構都是分子設計中不可或缺的一環,對比於步驟複雜需要事先合成許多前置化合物的傳統合成方法,本文將介紹具有步驟經濟效益且具高度選擇性的方法學來合成有機光電材料中的π-A-π結構,也就是利用鈀催化直接芳香環化反應達到此目的,此方法可以將傳統方法的四步合成減少至一步合成,大幅減少反應路徑,並在經過各式酸、配位基、反應時間、鹼以及溶劑的篩選後得到最佳化反應條件。而為了證明此條件的廣泛度以及適用性,於此嘗試各種拉電子基團 (Acceptor) 與芳香雜環的變化且可成功合成各類型π-A-π結構,證實此反應條件廣闊的應用性。
本實驗所合成的π-A-π結構具有可以做為後續反應位置的氫,藉由接上不同的功能性分子,可以使其應用在有機光伏電池 (OPVCs)、有機場效電晶體 (OFETs)、有機發光二極體 (OLEDs) 與染料敏化太陽能電池 (DSSCs) 之中,而本研究將以一鍋化的方式合成有機染料分子,並應用在染料敏化太陽能電池 (DSSCs) 上,合成出一條新結構的D-π-A-π-A’的產物CYL-11,並測得其能源轉換效率 (PCE) 為3.15 %
摘要(英) A Pd-catalyzed C-H (hetero) arylation methodology is well optimized for the efficient synthesis of versatile π-A-π type building blocks required in different organic electronic materials. This report not only provides a broad substrate scope of target π-A-π type building blocks but reduces the synthetic steps from four steps to a single step. After the reaction finish, it remains two possible positions for further arylable C-H bonds generated. By coupling with different types of functional groups, various types of organic electronic materials can be synthesized easily. For applications in dye-sensitized solar cells (DSSCs), we demonstrate that one D-π-A-π-A’ type new organic sensitizer (CYL-11) can be step-economically synthesized by using the one-pot condition which is adjusted from our best reaction condition. CYL-11 gives a Voc of 0.66 V, a Jsc of 6.61 mA/cm2, and the FF of 72.3 %, which corresponds to an overall power conversion efficiency (PCE) of 3.15 %. This work is expected to become a practical synthetic alternative aiming at guiding material scientists to access small-molecule materials of interest with less synthetic transformations.
關鍵字(中) ★ 鈀催化
★ 碳氫鍵活化
★ 有機光電材料
★ 位向選擇性
關鍵字(英) ★ Pd-catalyzed
★ C-H arylation
★ Regioselective
論文目次 目錄
一、緒論 - 1 -
1-1 π-A-π結構在小分子有機太陽能光伏電池的應用 - 3 -
1-2 π-A-π結構在高分子有機光伏電池的應用 - 6 -
1-3 π-A-π結構在有機場效電晶體的應用 - 9 -
1-4 π-A-π結構在染料敏化太陽能電池的應用 - 12 -
1-5 有機光電材料中π-A-π結構的合成 - 15 -
二、研究動機 - 18 -
三、結果與討論 - 21 -
3-1 尋找碳氫鍵芳香環化之最佳化操作條件 - 21 -
3-2 合成各式π-A-π核心 (π-Acceptor-π Cores) - 30 -
3-3 反應機制 - 41 -
3-4 π-A-π在染料敏化太陽能電池的合成與應用 - 44 -
3-5 結論與展望 - 54 -
四、儀器設備與藥品溶劑 - 56 -
4-1 實驗儀器 - 56 -
4-2 藥品與溶劑 - 60 -
五、合成步驟與化合物鑑定 - 61 -
5-1 General procedure A for Table 1: - 61 -
5-2 General procedure B for Table 2: - 64 -
5-3 Synthesis and characterization of compounds 4a and CYL-11 (Scheme 2): - 91 -
5-4 General Procedure D: Knoevenagel condensations - 94 -
參考文獻 - 96 -
NMR圖譜 - 102 -
參考文獻 參考文獻
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指導教授 劉青原(Ching-Yuan Liu) 審核日期 2016-8-30
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