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多環芳香烴-吡啶混成分子的合成及螢光特性研究 = Synthesis a...

國立高雄大學應用化學系碩士班

多環芳香烴-吡啶混成分子的合成及螢光特性研究 = Synthesis and Characterization of Polycyclic AromaticHydrocarbon∕Pyrrole Hybird Fluorophores

紀錄類型:	書目-語言資料,印刷品 : 單行本
並列題名:	Synthesis and Characterization of Polycyclic AromaticHydrocarbon∕Pyrrole Hybird Fluorophores
作者:	李長勳,
其他團體作者:	國立高雄大學
出版地:	[高雄市]
出版者:	撰者;
出版年:	2009[民98]
面頁冊數:	198面圖、表 : 30公分;
標題:	Paal-Knorr 縮合反應
標題:	Paal-Knorr Pyrrole synthesis
電子資源:	http://handle.ncl.edu.tw/11296/ndltd/76144272794747873405
附註:	指導教授：郭文章
附註:	參考書目：面
摘要註:	本論文研製之合成OLED 元件中的發光材料，以Paal-Knorr 縮合反應得到吡咯(pyrrole)主體結構，再將主體結構進行Buchwald-Hartwig 反應及Suzuki-Miyaura 交叉耦合反應，在2,5 號碳位置接上具有發光潛力的取代基，合成出六個吡咯螢光分子(2na-amine、2na-DMF、2na-pyrene、2na-naphthalene、2na-DPF、2na-spiro)及一個吡咯螢光分子原型(phenyl-DMF)。除了利用各種不同的合成方法得到吡咯的衍生物之外，另外也從材料的角度探討分子結構的不同對螢光特性的影響，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)等光譜鑑定其官能基的變化以及結構的形成。對於所發展出來之吡咯螢光分子在有機發光二極體方面的應用評估本研究利用UV 吸收及FL 放射光譜等瞭解分子的光學特性、利用TGA 及DSC 測量螢光分子的熱穩定性以及材料的形態穩定等特性，同時利用循環電位儀(CV)測量螢光分子的電化學性質以及HOMO/LUMO 能階。研究結果顯示這類螢光分子其光色不僅可控制在藍光的應用範圍，所得到螢光效率亦可大幅地提高，尤其是當結構中導入芴分子的螢光分子2na-DMF、2na-DPF 及2na-spiro(φf>0.99)。另外，在材料的熱性質方面，這些螢光材料不僅可形成穩定的玻璃態外，其玻璃轉移溫度最高甚至可達220℃（2na-spiro），且其熱裂解溫度可達500℃左右，顯現這類螢光分子具有良好的熱穩定性。而經由電化學性質，此系列螢光分子具有電洞傳遞特性，配合UV 光譜的能階計算可知這些材料的HOMO 能階座落在5.04~5.35 eV，而LUMO 能階則座落在1.9~2.0 eV，顯示這類螢光分子具有作為非摻雜型螢光材料或是磷光材料的主發光層等應用的潛力。在本研究中除了開發新的螢光材料之外，我們也嘗試探討分子結構的變化對螢光特性的影響。過程中發現：當螢光分子2na-DMF、2na-DPF 及2na-spiro 導入具螢光特性的芴分子取代基，其量子螢光效率進行大幅率提升，而且其Tg 點也提升到158、191及220℃，顯示在芳香取代吡咯的周圍導入多環芳香烴結構不僅可提高材料的熱性質，對於螢光效率也有大幅的提升；而在吡咯主體上3,4 號碳的位置上的作結構的改變後螢光分子phenyl-DMF、2na-DMF 的分子螢光效率分別為0.97 及＞0.99。顯示吡咯螢光分子周圍芳香取代基可有效的防止吡咯螢光分子產生團聚現象，達到提高螢光效率的目的。另外，研究中也發現提高材料的分子量、改變結構的剛硬性對於螢光分子的熱性質均能有效地提升。當導入芳香胺取代基時，2na-amine 螢光效率雖然無法有效提升，但可使螢光分子的HOMO 能階有效地下降。在整個研究中2na-spiro 具有最高的螢光效率（>0.99），熱裂解溫度540℃，玻璃轉移溫度220℃。顯示此螢光分子在螢光材料的應用上深具潛力，同時也顯示研究設計的方向是一可達到提高螢光特性的思考模式。 An aryl-substituted pyrrole was synthesized by means of Paal-Knorr pyrrole synthesis reaction. Through incorporating the aryl-substituted pyrrole moiety with a variety of poly-cyclic aromatic hydrocarbons via Buchwald-Hartwig reaction and Suzuki-Miyaura cross coupling reaction, a series of novel aryl-substituted polycyclic aromatic hydrocarbon/pyrrole hybrid fluorophores (2na-amine, phenyl-DMF, 2na-DMF, 2na-pyrene, 2na-naphthalene, 2na-DPF, 2na-spiro) were obtained. These fluorescent molecules were identified by NMR and Mass spectra. The OLED application potential of the fluorescent molecules was assessed in the as-pects of the photopysical properties, thermal stabilities and electrochemical behaviors. Pho-tophysical properties of the fluorophores were characterized from UV-visible and Fluores-cence spectra. Thermal properties of the pyrrole fluorophores were investigated by differen-tial scanning calorimetry (DSC) and thermogravimetric analysis (TGA). Cyclic voltammetry (CV) was employed to investigate the electrochemical behaviors of these fluorophores. In this work, most of the pyrrole fluorophores emitted blue light and possessed high quantum efficiency. Fluorescence properties of these pyrrole fluorophores were induced by ma-nipulating the surrounding aryl groups. By grafting highly fluorescent moiety (such as fluo-rene) onto the pyrrole, fluorophores 2na-DPF、2na-DMF and 2na-spiro exhibited highly fluorescence efficiency (f>0.99). Stable glassy thin-films could be obtained from all of the pyrrole fluorophores. The glass transition temperature of the fluorophore 2na-spiro was as high as 220oC. Moreover, the pyrrole fluorophores possessed high thermal decomposition temperatures (Td > 500 °C). These results indicated that these fluorophore possessed excel-lent thermal stability. The HOMO levels of the pyrrole fluorophores were estimated to be around 5.04~5.35 eV, whereas the LUMO levels were estimated to be around 1.9~ 2.0 eV. This result implies that the fluorophores may be used as the emission layer for the fluores-cence devices or as the host for the phosphorescence devices. In this work, the relationship between the chemical architecture and electrooptical properties was also studied. Variation of peripheral aromatic substitutions and the pyrrole structure would strongly affect the optical properties and thermal properties. Rigidity and highly fluorescent fluorene made the fluorophores 2na-DPF、2na-DMF and 2na-spiro pos-sessing high fluorescence quantum yields and stable thermal properties. Moreover, the cowded pyrrole structure made the fluorophore 2na-spiro and 2na-DPF possess higher quantum yield the fluorophore phenyl-DMF does. It is also important to note that the glass transition temperature and degradation temperature could be enhanced via increasing, mo-lecular weight and/or the rigidity of the substituent.

多環芳香烴-吡啶混成分子的合成及螢光特性研究 = Synthesis and Characterization of Polycyclic AromaticHydrocarbon∕Pyrrole Hybird Fluorophores
李, 長勳

多環芳香烴-吡啶混成分子的合成及螢光特性研究 = Synthesis and Characterization of Polycyclic AromaticHydrocarbon∕Pyrrole Hybird Fluorophores / 李長勳撰 - [高雄市] : 撰者, 2009[民98]. - 198面 ; 圖、表 ; 30公分.
指導教授：郭文章參考書目：面.
Paal-Knorr 縮合反應Paal-Knorr Pyrrole synthesis

多環芳香烴-吡啶混成分子的合成及螢光特性研究 = Synthesis and Characterization of Polycyclic AromaticHydrocarbon∕Pyrrole Hybird Fluorophores
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