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首页> 外文期刊>Carbon: An International Journal Sponsored by the American Carbon Society >The nano necklace made of single-walled carbon nanotubes and an azo-containing polymer: Island-like carboxyl distribution, bead-like morphology formation, and photophysical properties manipulation
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The nano necklace made of single-walled carbon nanotubes and an azo-containing polymer: Island-like carboxyl distribution, bead-like morphology formation, and photophysical properties manipulation

机译：由单壁碳纳米管和含偶氮聚合物制成的纳米项链：岛状羧基分布，珠状形态形成和光物理性质操纵

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摘要

The formation of a bead-shaped microstructure of poly{[3-octylthiophene-2,5-diyl]-[p-amino-azo-benzylidenequinomethane]}bonded SWNT (PDTAABQ-SWNT) reveals the inhomogeneous distribution of reactive sites along a SWNT in a covalent functionalization. The bead-shaped microstructure arises from the twisting and entangling of polymer chains due to spatial confinement and geometrical restriction, as a result of dense functionalization into island-like small areas containing a high density of carboxyl groups on the SWNT sidewall. Accordingly a portion of (Ca. 24.14%) trans-azobenzene side groups of PDTAABQ are forced to isomerize to the cis form due to a steric effect arising from the overcrowded environment in the 'bead'. The experimental findings are well-correlated with the molecular simulation, particularly for the physical realization of a bead-shaped microstructure and a trans-cis isomerization. The distortion in morphology due to the inhomogeneous distribution of reactive sites leads to a method for controlling the electronic structure and photophysical properties of SWNT. The transient optical properties of PDTAABQ-SWNT show a faster decaying component on a picosecond timescale but a very unusual slower decaying tail on a nanosecond timescale as compared to the timescale of the parent polymer (PDTADBQ). The severely distorted polymer chains with cis azobenezene side groups result in the reduction of the exciton mobility, leading to the longer fluorescence lifetime. This is confirmed by a similar ratio of the undepleted photoexcitons after 2.2 ns (Ca. 23.28%) and the ratio of the severely distorted polymers (Ca. 24.14%). (C) 2016 Elsevier Ltd. All rights reserved.
机译：聚{[3-辛基噻吩-2,5-二基]-[对氨基-偶氮-苄叉亚甲基喹啉甲烷]}键合的SWNT（PDTAABQ-SWNT）的珠状微观结构的形成揭示了沿SWNT的反应位点分布不均匀共价功能化。由于空间限制和几何限制，聚合物链的扭曲和缠结产生了珠状的微观结构，这是由于密集功能化为SWNT侧壁上包含高密度羧基的岛状小区域的结果。因此，由于“珠子”中过度拥挤的环境引起的空间效应，PDTAABQ的一部分（约24.14％）反式偶氮苯侧基被迫异构化为顺式。实验结果与分子模拟具有良好的相关性，特别是对于珠状微结构和反式顺式异构化的物理实现。由于反应位点的不均匀分布而导致的形貌畸变导致控制SWNT的电子结构和光物理性质的方法。与母体聚合物（PDTADBQ）的时间尺度相比，PDTAABQ-SWNT的瞬态光学特性在皮秒的时间尺度上显示出更快的衰减分量，而在纳秒的时间尺度上表现出非常不寻常的慢衰变尾巴。具有顺式偶氮苯的侧基的严重扭曲的聚合物链导致激子迁移率降低，从而导致更长的荧光寿命。 2.2 ns后未耗尽的光激子的比率（约23.28％）和严重变形的聚合物的比率（约24.14％）相似，证实了这一点。 （C）2016 Elsevier Ltd.保留所有权利。

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