固定發光中心之聚三烷基噻吩衍生物的合成 --

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题名:	固定發光中心之聚三烷基噻吩衍生物的合成 --
作者:	蕭乃綾;Nai-Ling Siao
贡献者:	化學研究所
关键词:	聚噻吩;固定發光中心;polythiophene;nonconjugated polymer
日期:	2005-06-29
上传时间:	2009-09-22 10:13:27 (UTC+8)
出版者:	國立中央大學圖書館
摘要:	顯示器科技快速發展，使得共軛高分子成為最受矚目的材料之一，因其除了易加工外，尚可藉由改變分子結構而發出不同的光色。其中聚塞吩衍生物具有結構多變性及良好的環境安定性，且可經由改變主鏈或支鏈的結構，有效的調整其放光顏色而受到學界的重視，成為探討結構與光色關係的模型材料。本研究利用Stille Coupling 合成一系列具有不同長度的飽和碳氫阻隔個別 Chromophore 的聚三烷基塞吩衍生物: Poly(3-octyl-2-(3-octyl-oligothiophen-2-yl)-5-alkylene- thiophene) (alkylene: methylene, propylene, 及hexylene) (oligothiophene : dimer, trimer, tetramer)，並以其UV-Vis及PL光譜來分析其光學性質。實驗顯示三個飽和碳氫鍵即可達到完全阻隔Chromophore間的?電子傳遞;而以一個飽和碳鏈阻斷Chromophore的高分子結構中，Chromophore為二個、三個及四個辛烷基塞吩環之高分子膜分別發出藍光、藍綠光及綠光，而三個飽和碳氫阻斷Chromophore的高分子中，兩個及三個辛烷基塞吩環之發光光色分為藍光及藍綠光。由此可知經由控制Chromophore的辛烷基塞吩環數及中間阻隔的飽和碳鏈長度，可合成發不同光色的高分子，提供了設計合成PLED發光材料的參考。此外我們也發現用飽和碳鏈將chromophore串成高分子後不但可增加其加工性並可增加量子產率。 Electroluminescent devices using conjugated polymer as a emitting layer have attracted much attention because of their academic interests and the potential utility of this technology in a wide variety of applications such as large area flat-panel displays and light-emitting diodes. Among conjugated polymers, polythiophenes are very attractive due to their high environmental stability and easy in structure modifications. A strategy was made to isolate the well-defined structure of chromophore in a polymer chain. The polymers prepared contain alternative non-conjugated spacer and conjugated chromophore. The non-conjugated aliphatic spacer could interrupt the transfer of electrons between the chromophores, therefore, the degree of conjugation of chromophores is fixed. A series of polythiophene derivatives containing alternating conjugated oliog-thiophene chromophores and non-conjugated aliphatic spacers were synthesized by a well-known Stille coupling reaction. The aliphatic spacers in the main chain were methylene, propylene, and hexylene. The polymers were amorphous and showed good solubility in common organic solvents. They were characterized by 1H-NMR, FT-IR, EA, gel permeation chromatography (GPC), thermogravimetric analysis (TGA), differential scanning calorimeter (DSC), UV-Vis absorption, and photoluminescence. It was found that propylene spacer could interrupt the transfer of the π-electrons between chromophores totally. Polymers containing di- and tri-thiophene as chromophores and propylene as a spacer displayed blue and greenish-blue emission in the solid-state. Furthermore, this type of polymer not only has good processability but also showed a better quantum yield compared to the small molecules with the same chromophore structures. This study provide a cue to design the materials for PLED (polymer light-emitting diode).
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