Single-Molecule Observation of Redox Reactions Enabled by Rigid and Isolated Tripodal Molecules
Single-Molecule Observation of Redox Reactions Enabled by Rigid and Isolated Tripodal Molecules
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DOI：
10.1021/acs.jpcc.2c07362
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发表时间：
2022-12-15
影响因子：
3.7
通讯作者：
Kim，Yousoo
中科院分区：
文献类型：
--
作者：
Kobayashi，Yuzu;Yokota，Yasuyuki;Kim，Yousoo
跟踪各种化学反应，包括单分子水平上的电化学和光化学反应，预计将从基础和应用方面产生大量知识。在这项研究中，我们报告了一种使用电化学扫描隧道显微镜（EC-STM）在单分子水平上追踪氧化还原反应的电子态变化的方法。 EC-STM 对于氧化还原反应的单分子分析非常强大，但之前的研究表明，由于氧化还原反应过程中的取向变化，很难分离结构和电子贡献。在这里，我们通过使用 EC-STM 合成和制造基于三蝶烯的结构刚性三足分子单层，可视化与氧化还原反应相关的单一二茂铁的电子态变化，该分子充当理想的锚，以保持电极和二茂铁部分之间的恒定距离。这种方法为固液界面重要现象（例如光化学和多相催化）的多功能单分子测量铺平了道路。
Tracking various chemical reactions, including electrochemical and photochemical reactions at the single-molecule level, is expected to yield a great deal of knowledge from both fundamental and applied aspects. In this study, we report on a methodology to track the electronic-state changes of redox reactions at the single-molecule level by using electrochemical scanning tunneling microscopy (EC-STM). EC-STM is powerful for single-molecule analysis of redox reactions, but previous studies have shown difficulties separating the structural and electronic contributions due to orientational changes during the redox reaction. Here, we visualize the electronic-state changes of a single ferrocene associated with redox reactions using EC-STM by synthesizing and fabricating a monolayer of structurally rigid tripodal molecules based on triptycene, which act as ideal anchors to preserve a constant distance between the electrode and the ferrocene moieties. This methodology paves the way for versatile single-molecule measurements of important phenomena at the solid–liquid interface, such as photochemistry and heterogeneous catalysis.