Two‐dimensionally extended aromatic polyamines for optimization of charge‐transporting properties by partial oxidation
Two‐dimensionally extended aromatic polyamines for optimization of charge‐transporting properties by partial oxidation
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DOI：
10.1002/pola.23510
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发表时间：
2009-09
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通讯作者：
T. Michinobu;Fumiaki Kato;J. Inui;H. Nishide
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作者：
T. Michinobu;Fumiaki Kato;J. Inui;H. Nishide
本文介绍了通过三仲胺单体与对苯二胺基二溴化物之间的缩聚反应合成二维延伸的芳香族多胺，通过化学和电化学氧化产生多自由基，以及空穴传输性能。多胺3a和3b的分子量（Mn）分别为7700和5000，并且两种聚合物在典型的有机溶剂中是非常可溶的，通过旋涂技术确保了良好的成膜能力。热重分析（TGA）和差示扫描量热法（DSC）表明，芳香族多胺的热稳定性相当高。更重要的是，交叉共轭结构对于受控的自由基生成和自由基稳定性的维持是必不可少的。在1体积%的三氟乙酸和部分氧化的多胺与NOPF 6的价间带的存在下的中性多胺的循环伏安图显示，所产生的自由基离域的对苯二胺部分。即使在环境条件下，聚自由基的半衰期也约为12小时，这使得我们能够制造和测量空穴器件。的电荷传输性能的聚胺显着改变的部分氧化（20摩尔%/铵单元）与NOPF 6。中性多胺表现出传统的注入限制行为，而多自由基的空穴传输行为是体限制的，并且高度依赖于化学结构。3b的聚自由基第一次实现了全共轭聚（铵阳离子自由基）的有效空穴传输。© 2009 Wiley Periodicals，Inc.聚合物科学杂志A部分：聚合物化学47：4577-4586，2009
This article describes the synthesis of the two-dimensionally extended aromatic polyamines by polycondensation between the tri-sec-amine monomer and p-phenylenediamine-based dibromide, the polyradical generation by chemical and electrochemical oxidations, and the hole-transporting properties. The molecular weights (Mn) of the polyamines, 3a and 3b, were 7700 and 5000, respectively, and both polymers were very soluble in the typical organic solvents, ensuring a good film formation capability by a spin-coating technique. The thermal stability of the aromatic polyamines, elucidated by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC), was quite high. More important, the cross-conjugated structure is essential for the controlled radical generation and the maintenance of the radical stability. Cyclic voltammograms of the neutral polyamines in the presence of 1 vol % of trifluoroacetic acid and the intervalence bands of the partially oxidized polyamines with NOPF6 revealed that the generated radicals delocalize over the p-phenylenediamine moieties. The half-life of the polyradicals was about 12 h even under ambient conditions, which allowed us to fabricate and measure the hole-only devices. The charge-transporting properties of the polyamines were dramatically changed by the partial oxidation (20 mol %/aminium unit) with NOPF6. The neutral polyamines showed the conventional injection-limit behaviors, whereas the hole-transporting behaviors of the polyradicals are bulk-limit and highly dependent on the chemical structure. The efficient hole-transport of the all-conjugated poly(aminium cationic radical)s was for the first time realized for the polyradical of 3b. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 4577–4586, 2009