新型側鏈含蒽胺發光團芳香族高分子之合成與光致發光及電化學性質之研究

Synthesis, Photoluminescence and Electrochemical Properties of Novel Aromatic Polymers Bearing Anthrylamine Chromophores

顏宏儒(Hung-Ju Yen)

指導教授 ： 劉貴生

國立暨南國際大學/科技學院/應用化學系/碩士(2007年)

摘要

9-[N,N-di(4-carboxyphenyl)amino]anthracene是由對氟苯腈與9-蒽胺進行親核性取化反應生成腈基化合物，隨後此二腈中間物以鹼性水解而致使一新型含蒽胺的二羧酸單體化合物的產生。N-(4-Aminophenyl)phenothiazine是由對氟硝基苯與酚噻嗪進行親核性取代反應生成硝基化合物，接著再用聯胺與鉑金屬催化還原而被合成出。更進一步的與對氟硝基苯進行胺基化反應，隨後將二硝中間物還原而獲得一個新型含酚噻嗪的二胺單體化合物[4,4’-diamino-4”-N-phenothiazinyltriphenylamine]。
本論文分成三個部分，包含了以9-[N,N-di(4-carboxyphenyl)amino]anthracene為主體所合成出的二個系列新型含蒽胺之芳香族聚(胺-醯胺) 和聚(胺-1,3,4,-噁二唑)，以及第三個部分以4,4’-diamino-4”-N-phenothiazinyltriphenylamine為主體所合成出的一系列新型含酚噻嗪之芳香族聚(胺-醯胺)。這三個系列新型具蒽胺與酚噻嗪側鏈基團之芳香族高分子之合成與基本特性、光致發光、電化學及電致變色性質已被分別研究與比較。所有的高分子不僅在極性非質子型溶劑中有好的溶解性，出色的薄膜成形能力，高的玻璃轉換溫度、軟化溫度、好的熱穩定性、較低的HOMO能階，而且部分高分子也展現好的光致發光及出色可逆的電致變色特性。如此，這些含蒽胺的新型高分子由於適當的HOMO值和出色熱穩定性、螢光量子效率及電化學不僅能被做為P-LED的電洞傳輸層和綠色發光材料，而且也可應用於新型的電致變色元件；這些含酚噻嗪的高分子由於適當的HOMO值和出色的電化學及熱穩定性也許能被廣泛的應用在P-LED當電洞傳輸層和電致變色的材料。

關鍵字

蒽酚噻嗪聚(胺-醯胺) ； 聚(胺-1,3,4,-噁二唑) ； 光致發光 ； 電化學 ； 電致變色 ； 芳香族高分子

並列摘要

The newly anthrylamine-based aromatic dicarboxylic acid, 9-[N,N-di(4-carboxyphenyl)amino]anthracene, was successfully synthesized by the sodium hydride-mediated condensation of 9-aminoanthracene with 4-fluorobenzonitrile, followed by the alkaline hydrolysis of the dinitrile intermediate led to a newly anthrylamine-based aromatic dicarboxylic acid. N-(4-Aminophenyl)phenothiazine was prepared by the cesium fluoride-mediated aromatic nucleophilic substitution reaction of phenothiazine with 4-fluoronitrobenzene followed by hydrazine Pd/C-catalytic reduction. Further amination reaction between N-(4-aminophenyl)phenothiazine with 4-fluoronitrobenzene, subsequent reduction of the dinitro intermediate obtained to the new phenothiazine-containing aromatic diamine, 4,4’-diamino-4”-N-phenothiazinyltriphenylamine.
This study has been separated into three parts. Part I and II include two series of novel aromatic poly(amine-amide)s and poly(amine-1,3,4-oxadiazole)s based on 9-[N,N-di(4-carboxyphenyl)amino]anthracene. Part III included a series of novel aromatic poly(amine-amide)s based on 4,4’-diamino-4”-N-phenothiazinyltriphenylamine. The synthesis, basic characterization, photoluminescence, electrochemical and electrochromic properties of three series of novel aromatic polymers bearing pendent anthrylamine and phenothiazine groups were investigated and compared, respectively. All polymers had good solubility in many polar aprotic solvents, and exhibited excellent thin-film-forming ability. In additional to high Tg or Ts values, good thermal stability, and lower HOMO energy levels, some of polymers also exhibited good photoluminescent and excellent reversibility of electrochromic characteristics. Thus, these novel anthrylamine-containing polymers can be considered not only as hole-transporting layer and green light-emitting materials in P-LED but also could be widely applied as a new electrochromic devices due to their proper HOMO values, excellent thermal stability, fluorescence quantum efficiency and good electrochemical behavior; these phenothiazine-containing polyamides may be widely applied in P-LED as hole-transporting layer and electrochromic materials due to their proper HOMO values, excellent electrochemical and thermal stability.

並列關鍵字

anthracene ； phenothiazine ； poly(amine-amide)s ； poly(amine-1,3,4-oxadiazole)s ； photoluminescence ； electrochemical ； electrochromic ； aromatic polymers

參考文獻

REFERENCES AND NOTES for Part I

(6) Jenekhe, S. A.; Lu, L.; Alam, M. M. Macromolecules 2001, 34, 7315.

(7) Cheng, S. H.; Hsiao, S. H.; Su, T. H.; Liou, G. S. Macromolecules 2005, 38 ,307.

(8) Nguyen, T. Q.; Martini, I. B.; Liu, J.; Scgwartz, B. J. J. Phys. Chem. B 2000, 104, 237.

(9) Meskers, S. C. J.; Janssen, R. A. J.; Haverkort, J. E. M. Chem. Phys. 2000, 260, 415.