具有3,6-雙(第三丁基)唑取代的三苯胺基團之新型芳香族聚合物的合成與光致發光及電致變色性質之研究

一種由唑(carbazole)所衍生的新型含三苯胺結構的二羧酸單體4,4’-dicarboxy-4”-(3,6-di-tert-butylcarbazol-9-yl)triphenylamine是從現有的試劑利用已知的化學反應合成而得。此新單體各別與芳香族二胺、二醯(dihydrazides)及對胺基苯醯(p-aminobenzoyl hydrazide)反應製得一系列新型主鏈上具有3,6-di-tert-butylcarbazol-9-yl 取代的三苯胺基團的聚醯胺、聚醯(polyhyrazides)及聚醯胺-醯[poly(amide-hydrazide)]。這些聚合物很容易溶解在極性的有機溶劑中，並可經由他們的溶液塗佈鑄成可撓曲性及強韌的薄膜。其中含醯基的聚合物可在高溫下進一步轉化成具噁二唑基的聚合物(oxadiazole polymers)。這些高分子除了有高的玻璃轉移溫度(Tg)及良好的熱穩定性，所有的聚合物在溶液中或薄膜型態都表現出強的螢光特性且有高的量子效率。這些高分子經由循環伏安法測定均有兩對可逆的氧化還原峰。當與唑不含tert-butyl取代基的相似聚合物比較時，在唑結構的活性位置(3及6)上導入巨大的tert-butyl取代基會賦予這些聚合物更好的電化學安定性。此外，這些聚合物也具有良好的電致變色特性，他們的薄膜顏色可從中性態的無色或淡黃色轉變成半氧化態的綠色及完全氧化的藍色。

關鍵字

電致變色；光致發光

並列摘要

A new carbazole-derived, triphenylamine-containing aromatic dicarboxylic acid monomer, 4,4’-dicarboxy-4”-(3,6-di-tert-butylcarbazol-9-yl)triphenylamine, was synthesized by a well known chemistry from readily available reagents. The newly synthesized dicarboxylic acid monomer was reacted with various aromatic diamines, dihydrazides, and p-aminobenzoyl hydrazide to produce of novel series of polyamides, polyhydrazides and poly(amide-hydrazide) with 3,6-di-tert-butylcarbazol-9-yl-substituted triphenylamine units in the backbones. All the resulting polymers were readily soluble in polar organic solvents and could be solution-cast into tough and flexible films. The hydrazide polymers could be further converted into the corresponding oxadiazole polymers at elevated temperatures. Apart from high Tg values and good thermal stability, all the obtained polymers exhibited strong fluorescence both in film and in solution with high quantum yield. All the polymers showed two reversible oxidation redox couples on their cyclic voltammograms. By substitution of the electrochemically active C3 and C6 sites of the carbazole unit with bulky tert-butyl groups, the new polymers exhibit greatly enhanced electrochemical stability in comparison with previously reported analogs without tert-butyl substituents on the carbazole moiety. The polymer films also revealed excellent stability of electrochromic characteristics with coloration change from a colorless or pale yellowish neutral state to green as a radical cation and blue when fully oxidized.

並列關鍵字

Electrochromism ； Photoluminescence

參考文獻

5. Beaujuge, P. M.; Reynolds, J. R. Chem. Rev. 2010, 110, 268.

11. (a) Thelakkat, M. Macromol. Mater. Eng. 2002, 287, 442. (b) Shirota, Y.; Kageyama, H. Chem. Rev. 2007, 107, 953.

14. (a) Cheng, S.-H.; Hsiao, S.-H.; Su, T.-H.; Liou, G.-S. Macromolecules 2005, 38, 307. (b) Hsiao, S.-H.; Chang. Y.-M.; Chen, H.-W.; Liou, G.-S. J. Polym. Sci. Part A: Polym. Chem. 2006, 44, 4579. (c) Liou, G.-S.; Hsiao, S.-H.; Huang, N.-K.; Yang, Y.-L. Macromolecules 2006, 39, 5337. (d) Chang, C.-W.; Liou, G.-S.; Hsiao, S.-H. J. Mater. Chem. 2007, 17, 1007. (e) Hsiao, S.-H.; Liou, G.-S.; Kung, Y.-C.; Yen, H.-J. Macromolecules 2008, 41, 2800. (f) Kung, Y.-C.; Liou, G.-S.; Hsiao, S.-H. J. Polym. Sci. Part A: Polym. Chem. 2009, 47, 1740. (g) Hsiao, S.-H.; Liou, G.-S.; Wang, H.-M. J. Polym. Sci. Part A: Polym. Chem. 2009, 47, 2330.

18. Yang, C.-P.; Chen, R.-S.; Chen, K.-H. Colloid Polym. Sci. 2003, 281, 505.

20. Demas, J. N.; Crosby, G. A. J. Phys. Chem. 1971, 75, 991.

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具有3,6-雙(第三丁基)唑取代的三苯胺基團之新型芳香族聚合物的合成與光致發光及電致變色性質之研究

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