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系統識別號 U0026-2807201711521700
論文名稱(中文) 苉及二苯并[a,l]稠四苯衍生物-合成與性質分析
論文名稱(英文) Synthesis and Properties of Picene and Dibenzo[a,l]tetracene Derivatives
校院名稱 成功大學
系所名稱(中) 化學系
系所名稱(英) Department of Chemistry
學年度 105
學期 2
出版年 106
研究生(中文) 王毓婷
研究生(英文) Yu-Ting Wang
學號 L36041115
學位類別 碩士
語文別 中文
論文頁數 90頁
口試委員 指導教授-吳耀庭
口試委員-劉青原
口試委員-徐秀福
口試委員-曾瑞昌
中文關鍵字   超導性  有機場效應電晶體  π-共軛系統分子  稠四苯  有機發光二極體  光電性質 
英文關鍵字 pi conjugated system  picene  Bromo  derivatives  acene  tetracene  dibenzo  iron Catalysis 
學科別分類
中文摘要 Part 1
苉衍生物-合成與性質分析
苉(Picene),是含有五個苯環以扶手椅排列形式(Z字型)堆疊而成之高度共軛系統分子,由於其特殊結構,該類化合物在有機場效應電晶體(OFET)及有機薄膜太陽能電池方面皆有良好的應用前途,所以如何高效率的合成其衍生物就吸引學者們的高度重視。但前人在合成上都有些缺點及限制,例如:使用昂貴的催化劑、照射波長的受限、合成步驟繁瑣…等。而本論文成功設計了有別於前人的合成手法,利用步驟簡單、條件溫和的方式合成出苉衍生物,並利用電化學實驗及光物理實驗得知化合物9及11之HOMO、LUMO能階及螢光放光的不同。
雖然本論文成功利用簡單溫和的條件合成出苉衍生物,但在嘗試延伸π-共軛系統時遇到了困難,更換了許多種合成路徑都無法得到期望的化合物26及39,所以如何克服及改善其π-共軛系統延伸所遇到的問題是將來可以繼續發展的重點。

Part 2
二苯并[a,l]稠四苯衍生物-合成與性質分析
由於OLED所製成之元件,具有高亮度、高發光效率以及低功率消耗…等優點,所以在業界、學界奠定了重要的地位。因具有剛硬的分子結構其相對放螢光效率就會提高,所以可當成有機發光二極體的元件,如并苯。并苯(acenes)為若干個苯環在對邊稠合之多環芳香烴,而大分子量並苯則具有潛在的光電性質。本論文合成出二苯并[a,l]稠四苯(44)與其衍生物(化合物45),並利用電化學實驗及光物理實驗得知其HOMO、LUMO能階及螢光放光的不同。
雖然本論文成功合成二苯并[a,l]稠四苯(44)與其中之一衍生物(化合物45),但我們在嘗試合成其另一衍生物(化合物46)時遇到了困難,嘗試了許多種合成路徑都無法得到期望的化合物46,所以如何將關鍵步驟之化合物52a或45a結構中之甲氧基有效的轉換成甲基,是將來必須繼續發展的關鍵。
英文摘要 Part 1: Picene Derivatives –Synthesis and Properties
Polyaromatic compounds have an inevitable role in the material science, and among the picene compounds attract the great interest due to its numerous applications in material applications. In this research work, we have developed a viable synthetic strategy to picene derivatives. This newly developed methodology is entirely different from its predecessors and employed under mild reaction conditions. The notable features of this method include operationally simple reaction conditions, high yields and scalable to larger quantities. Also, we investigated the physiochemical properties of this newly prepared picene derivatives.

Part 2: Dibenzo[a,l]tetracene Derivatives –Synthesis and Properties
Acenes are polycyclic aromatic hydrocarbons consisting of linearly integrated benzene rings. The larger acenes are steadily receiving much attention as an active semiconducting material in organic field-effect transistors (OFETs) and organic light-emitting diodes (OLEDs) owing to its high charge-carrier mobility. In the view of increased conjugation length is presumed to be beneficial for some applications in organic electronics, interest in the synthesis of larger acenes has been increased in the recent years. Thus, the significant efforts have been devoted to the development of reliable synthetic methods for the larger acenes. However, the synthesis of larger and stable acenes is a challenging exercise because of their low solubility, poor light and oxygen stability, and tendency to dimerize, as well as the laborious multistep synthetic approaches required. In this study, we report the synthesis of new class of dibenzo[a,l]tetracene (44) and its larger derivatives (45). The reaction yield of dibenzo[a,l]tetracene (44) under mild reaction condition was much higher than the previous reports. The structure of the compounds confirmed with 1H, and 13C NMR spectroscopy and the photophysical studies were investigated.
論文目次 中文摘要...................................................................................................... I
英文延伸摘要......................................................................................... III
謝誌........................................................................................................... XIII
表目錄.................................................................................................... XVII
圖目錄................................................................................................... XVIII
Part 1: 苉衍生物-合成與性質分析............................................1
壹、前言...................................................................................................... 2
一、研究動機........................................................................................... 2
貳、結果與討論....................................................................................... 5
一、苉與其衍生物的合成反應.............................................................5
(一) 苉化合物3d之合成步驟................................................................ 5
(二) 苉衍生物化合物9, 11, 12之合成步驟.......................................... 7
二、光物理性質分析............................................................................ 11
三、電化學性質分析............................................................................ 12
四、嘗試合成苉衍生物化合物26.................................................... 13
(一)苉衍生物化合物26之合成設計.....................................................13
(二)合成起始物化合物24之方法........................................................ 14
五、嘗試延伸苉之π共軛系統.......................................................... 18
參、結論..................................................................................................... 20
肆、實驗..................................................................................................... 21
一、試劑名稱與縮寫對照表.............................................................. 21
二、實驗儀器及部分細節................................................................... 22
三、實驗操作.......................................................................................... 24
伍、參考文獻........................................................................................... 37
陸、附錄..................................................................................................... 39
一、核磁共振光譜圖............................................................................ 39
二、紫外可見光譜圖與螢光放射光譜圖..................................... 49
三、循環伏安法分析圖....................................................................... 50
Part 2: 二苯并[a,l]稠四苯衍生物-合成與性質分析....... 51
壹、前言..................................................................................................... 52
一、凱庫勒烯 (Kekulene)................................................................... 52
二、研究動機........................................... 53
貳、結果與討論...................................................................................... 54
一、二苯并[a,l]稠四苯與其衍生物的合成反應............................ 54
二、光物理性質分析............................................................................ 58
三、嘗試合成二苯并[a,l]稠四苯衍生物化合物46…............... 59
(一)使用鎳催化劑合成二苯并[a,l]稠四苯衍生物化合物46........... 59
(二)以合環產物合成二苯并[a,l]稠四苯衍生物化合物46........... 61
參、結論.......................................... 63
肆、實驗...................................... 64
一、試劑名稱與縮寫對照表.................................. 64
二、實驗儀器及部分細節................................... 65
三、實驗操作..................................... 67
伍、參考文獻...................................... 79
陸、附錄............................................ 81
一、核磁共振光譜圖..................................... 81
二、紫外可見光譜圖與螢光放射光譜圖........................ 90
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