Diarylethene Self-Assembled Monolayers: Cocrystallization and Mixing-Induced Cooperativity Highlighted by Scanning Tunneling Microscopy at the Liquid/Solid Interface.
Diarylethene Self-Assembled Monolayers: Cocrystallization and Mixing-Induced Cooperativity Highlighted by Scanning Tunneling Microscopy at the Liquid/Solid Interface.
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DOI：
10.1002/chem.201500804
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发表时间：
2015-08
期刊：
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通讯作者：
Denis Frath;Takeshi Sakano;Yohei Imaizumi;S. Yokoyama;T. Hirose;K. Matsuda
中科院分区：
文献类型：
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作者：
Denis Frath;Takeshi Sakano;Yohei Imaizumi;S. Yokoyama;T. Hirose;K. Matsuda
表面上二维多组分分子有序的刺激控制是实现具有刺激响应表面性能的先进材料的关键技术。在辛酸/高取向热解石墨界面上，用扫描隧道显微镜观察了含二芳烯酰胺的二维分子有序的形成和光异构化过程，该酰胺在开环和闭环异构体之间进行了光异构化，并发生了副反应生成环状异构体。利用液/固界面协同模型分析了表面覆盖率的浓度依赖性，确定了成核（Kn）和延伸（Ke）平衡常数。发现环状异构体有一个很大的平衡常数，这解释了环状异构体主要观察到的顺序。同时发现闭环异构体的存在诱导协同作用形成由开环异构体组成的分子有序结构。利用合作模型对二维多组分分子有序的形成进行了定量分析，为研究分子有序的形成提供了新的视角。
Stimulus control over 2D multicomponent molecular ordering on surfaces is a key technique for realizing advanced materials with stimuli-responsive surface properties. The formation of 2D molecular ordering along with photoisomerization was monitored by scanning tunneling microscopy at the octanoic acid/highly oriented pyrolytic graphite interface for a synthesized amide-containing diarylethene, which underwent photoisomerization between the open- and closed-ring isomers and also a side-reaction to give the annulated isomer. The nucleation (Kn) and elongation (Ke) equilibrium constants were determined by analysis of the concentration dependence of the surface coverage by using a cooperative model at the liquid/solid interface. It was found that the annulated isomer has a very large equilibrium constant, which explains the predominantly observed ordering of the annulated isomer. It was also found that the presence of the closed-ring isomer induces cooperativity into the formation of molecular ordering composed of the open-ring isomer. A quantitative analysis of the formation of ordering by using the cooperative model has provided a new view of the formation of 2D multicomponent molecular ordering.