Self-Assembly of a Functional Oligo(Aniline)-Based Amphiphile into Helical Conductive Nanowires.
Self-Assembly of a Functional Oligo(Aniline)-Based Amphiphile into Helical Conductive Nanowires.
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DOI：
10.1021/jacs.5b06892
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发表时间：
2015-11-18
影响因子：
15
通讯作者：
Faul CF
中科院分区：
文献类型：
--
作者：
Bell OA;Wu G;Haataja JS;Brömmel F;Fey N;Seddon AM;Harniman RL;Richardson RM;Ikkala O;Zhang X;Faul CF
合成了一种四苯胺基阳离子两亲物TANI-NHC（O）C5H10N（CH3）3 + Br-（TANI-PTAB），并发现其翠绿亚胺碱（EB）态在水溶液中自组装成纳米线.所观察到的自组装描述的等键模型，所示的温度依赖性的紫外-可见光谱的调查。线性二色性（LD）的研究，结合计算模型，使用含时密度泛函理论（TD-DFT），表明TANI-PTAB分子在纳米线内的反平行排列，与TANI-PTAB的长轴垂直排列的纳米线长轴。向TANI-PTAB中添加S-或R-邻苯二磺酸（CSA）将TANI转化为翠绿亚胺盐（ES），其保留形成纳米线的能力。酸掺杂的TANI-PTAB的纳米线的形态有深远的影响，CSA抗衡离子的手性转化为螺旋扭曲的纳米线，如通过圆二色性（CD）观察。最后，从水溶液加工的CSA掺杂的螺旋纳米线薄膜的电导率为2.7 mS cm-1。导电性、对自组装一维结构的控制和水溶性证明了这些材料作为分子电子学、氧化还原控制材料和传感的可加工和可寻址功能材料的前景。
A tetra(aniline)-based cationic amphiphile, TANI-NHC(O)C5H10N(CH3)3+Br– (TANI-PTAB) was synthesized, and its emeraldine base (EB) state was found to self-assemble into nanowires in aqueous solution. The observed self-assembly is described by an isodesmic model, as shown by temperature-dependent UV–vis investigations. Linear dichroism (LD) studies, combined with computational modeling using time-dependent density functional theory (TD-DFT), suggests that TANI-PTAB molecules are ordered in an antiparallel arrangement within nanowires, with the long axis of TANI-PTAB arranged perpendicular to the nanowire long axis. Addition of either S- or R- camphorsulfonic acid (CSA) to TANI-PTAB converted TANI to the emeraldine salt (ES), which retained the ability to form nanowires. Acid doping of TANI-PTAB had a profound effect on the nanowire morphology, as the CSA counterions’ chirality translated into helical twisting of the nanowires, as observed by circular dichroism (CD). Finally, the electrical conductivity of CSA-doped helical nanowire thin films processed from aqueous solution was 2.7 mS cm–1. The conductivity, control over self-assembled 1D structure and water-solubility demonstrate these materials’ promise as processable and addressable functional materials for molecular electronics, redox-controlled materials and sensing.