楊吉水臺灣大學：化學研究所許哲維Hsu, Chi-WeiChi-WeiHsu2007-11-262018-07-102007-11-262018-07-102006http://ntur.lib.ntu.edu.tw//handle/246246/51765本論文中，我們利用Sonogashira 偶合反應合成兩系列具有 推拉電子共軛系統的苯炔烯類化合物，分別為1-phenylethynyl- 4-(trans-4-pyridylethenyl)benzene系列(1)及1-phenylethynyl-4-(trans- 2-pyridylethenyl)benzene系列(2)，並研究其光物理性質、電化學特性及電致化學發光性質（Electrogenerated ChemiLuminescence; ECL）。 此二系列化合物的UV-Vis吸收光譜、螢光放光光譜與電化學量測及電致化學發光實驗，均在乙腈溶液下量測。化合物1與2的UV-Vis吸收峰分布在335 nm到369 nm之間，螢光放光峰則分布在390 nm到550 nm之間，而其分布隨著分子極性的增加(即由a到e)而有紅位移的現象產生。化合物1和2中以b、c、d取代者，具有較好的螢光量子產率(ΦFlu)，其ΦFlu值均高於0.5，尤其又以2d為最高，為0.77。 在電致化學發光性質的研究方面，我們提供化合物溶液足夠的氧化及還原電位，再以ECL裝置分別記錄除氧條件下的ECL光譜。我們發現ECL光譜的分布集中在440 nm 到470 nm之間，只有化合物2e紅位移至540 nm。這種現象顯示了ECL對於分子極性改變的不敏感，我們認為在ECL的反應過程中涉及了二聚體(excited dimer)的發生。We have synthesized two series of donor-acceptor substituted pi-conjugated phenylvinylene/phenylethynylene systems by the Sonogashira coupling reactions : namely, the 1-phenylethynyl-4-(trans-4- pyridylethenyl)benzenes, (1), and the 1-phenylethynyl-4-(trans-2- pyridylethenyl)benzenes, (2). We report, in this dissertation, their synthesis, photophysical, electrochemical and Electrogenerated ChemiLuminescence(ECL) properties. All the measurements of UV-Vis absorption, fluorescence emission, electrochemistry, and ECL for 1 and 2 were carried out in acetonitrile solutions. The UV-Vis absorption maxima of 1 and 2 are between 335 and 369 nm, and their fluorescence emission maxima between 390 and 550 nm. Those with stronger donors (i.e., a＜b＜c＜d＜e) possess longer wavelengths of both the absorption and fluorescence maxima. The fluorescence spectra are more sensitive than the UV-Vis spectra to the nature of the donor group. All these compounds have high fluorescence quantum yield(ΦFlu), and amound them, 2d has the highest value(ΦFlu = 0.77). The ECL of 1 and 2 in outgassed acetonitrile solutions were measured under a condition in which the substrates can be reduced and oxidized. The ECL maxima are all in the range of 440-470 nm, except for 2e located at 540 nm. These observation indicate that the ECL of 1 and 2 are insensitive to position and nature of substituent. This can be attributed to the ECL emission from excited dimmers.目 錄 ………………………………………………………………Ⅰ 圖表目錄 ………………………………………………………………Ⅲ 附圖目錄 ………………………………………………………………Ⅴ 中文摘要 ………………………………………………………………Ⅷ 英文摘要 ………………………………………………………………Ⅸ 第一章 緒論……………………………………………………………1 1-1電致化學發光簡介 …………………………………………………1 1-2電致化學放光反應機制 ……………………………………………2 1-2-1 Ion annihilation ……………………………………………2 1-2-2 共試劑電致化學放光(Coreactant ECL) ……………………4 1-2-3 Preannihilation ECL…………………………………………6 1-3 電致化學放光的反應路徑…………………………………………6 1-3-1 S-route ………………………………………………………7 1-3-2 T-route ………………………………………………………8 1-3-3 E-route ………………………………………………………9 1-4 電致化學放光的應用 …………………………………………11 1-5 分子內電子轉移…………………………………………………13 1-6 研究動機…………………………………………………………14 第二章 結果與討論 …………………………………………………16 2-1化合物的設計………………………………………………………16 2-2化合物1及2的合成…………………………………………………17 2-3光物理性質…………………………………………………………19 2-4電化學性質…………………………………………………………23 2-5電致化學發光性質…………………………………………………26 2-6結論…………………………………………………………………34 第三章 實驗部份 ……………………………………………………35 3-1儀器部分……………………………………………………………35 3-2實驗步驟……………………………………………………………36 3-3合成步驟……………………………………………………………44 3-3-1催化劑Pd(PPh3)2Cl2的製備……………………………………44 3-3-2合成末端炔基化合物……………………………………………44 3-3-3起始物的製備……………………………………………………49 3-3-4合成雙鍵、三鍵系統的共軛化合物……………………………51 參考資料 ………………………………………………………………61 附圖 ……………………………………………………………………647104009 bytesapplication/pdfen-US電致化學發光推拉電子基苯乙烯吡啶ECLdonor-acceptorstilbazolethesishttp://ntur.lib.ntu.edu.tw/bitstream/246246/51765/1/ntu-95-R92223080-1.pdf