Chemical reactions that occur at nanostructured electrodes have garnered widespread interest because of their potential applications in fields including nanotechnology, green chemistry and fundamental physical organic chemistry. Much of our present understanding of these reactions comes from probes that interrogate ensembles of molecules undergoing various stages of the transformation concurrently. Exquisite control over single-molecule reactivity lets us construct new molecules and further our understanding of nanoscale chemical phenomena. We can study single molecules using instruments such as the scanning tunnelling microscope, which can additionally be part of a mechanically controlled break junction. These are unique tools that can offer a high level of detail. They probe the electronic conductance of individual molecules and catalyse chemical reactions by establishing environments with reactive metal sites on nanoscale electrodes. This Review describes how chemical reactions involving bond cleavage and formation can be triggered at nanoscale electrodes and studied one molecule at a time.

在纳米结构电极上发生的化学反应因其在纳米技术、绿色化学和基础物理有机化学等领域的潜在应用而受到广泛关注。我们目前对这些反应的大部分理解来自于询问同时经历不同转化阶段的分子集合的探针。对单分子反应性的精确控制使我们能够构建新分子并加深我们对纳米级化学现象的理解。我们可以使用扫描隧道显微镜等仪器研究单个分子，它还可以是机械控制断裂连接的一部分。这些是可以提供高水平细节的独特工具。他们通过在纳米级电极上建立具有活性金属位点的环境来探测单个分子的电子电导并催化化学反应。这篇综述描述了如何在纳米级电极上触发涉及键断裂和形成的化学反应，并一次研究一个分子。