In Situ Coupling of Single Molecules Driven by Gold‐Catalyzed Electrooxidation
In Situ Coupling of Single Molecules Driven by Gold‐Catalyzed Electrooxidation
复制标题
金催化电氧化驱动的单分子原位偶联
DOI：
10.1002/ange.201906215
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发表时间：
2019
影响因子：
--
通讯作者：
Venkataraman, Latha
中科院分区：
文献类型：
--
作者：
Zang, Yaping;Stone, Ilana;Inkpen, Michael S.;Ng, Fay;Lambert, Tristan H.;Nuckolls, Colin;Steigerwald, Michael L.;Roy, Xavier;Venkataraman, Latha
在扫描隧道显微镜(STM)的基础上发展了一种单分子方法来选择性偶联一系列苯胺衍生物并生成偶氮苯。Au催化的氧化偶联是由纳米结构Au STM尖端的局部电化学势驱动的。通过测量电导和分子结伸长对产物进行了原位检测，并与异地制备的预期偶氮苯衍生物的类似测量进行了比较。这种单分子方法是强大的，它可以快速和重复性地为各种苯胺产生反应。我们进一步展示了通过互补苯胺的顺序耦合选择性地合成几何异构体和组装复杂的分子结构，展示了在纳米尺度上对键形成的前所未有的控制。
A single‐molecule method has been developed based on the scanning tunneling microscope (STM) to selectively couple a series of aniline derivatives and create azobenzenes. The Au‐catalyzed oxidative coupling is driven by the local electrochemical potential at the nanostructured Au STM tip. The products are detected in situ by measuring the conductance and molecular junction elongation and compared with analogous measurements of the expected azobenzene derivatives prepared ex situ. This single‐molecule approach is robust, and it can quickly and reproducibly create reactions for a variety of anilines. We further demonstrate the selective synthesis of geometric isomers and the assembly of complex molecular architectures by sequential coupling of complementary anilines, demonstrating unprecedented control over bond formation at the nanoscale.