文献类型：期刊文献

英文题名：Electrocatalytic Benzylic C-H Activation Enables Direct Au-C Single-Molecule Junctions

作者：Ding, Canqiu[1,2];Chen, Jue[1,2];Zhu, Rongqin[1,2];Qiu, Jin[1,2];Zhang, Yutian[1,2];Li, Hongxiang[1,2];Zou, Qi[1,2];Tian, He[1,2]

机构：[1]East China Univ Sci & Technol, Inst Fine Chem,Key Lab Adv Mat, Frontiers Sci Ctr Materiobiol & Dynam Chem, Sch Chem & Mol Engn,Feringa Nobel Prize Scientist, Shanghai 200237, Peoples R China;[2]East China Univ Sci & Technol, Frontiers Sci Ctr Materiobiol & Dynam Chem, Sch Chem & Mol Engn,Inst Fine Chem,Feringa Nobel P, Joint Int Res Lab Precis Chem & Mol Engn, Shanghai 200237, Peoples R China

年份：2026

卷号：148

期号：15

起止页码：16192

外文期刊名：JOURNAL OF THE AMERICAN CHEMICAL SOCIETY

收录：;EI(收录号：20261720579784);WOS:【SCI-EXPANDED(收录号:WOS:001736588700001)】；

基金：This work was supported by the National Natural Science Foundation of China (grants 22335004, 22588101, 22475068, 52273176, and 22575084), the Fundamental and Interdisciplinary Disciplines Breakthrough Plan of the Ministry of Education of China (grant JYB2025XDXM404), the Science and Technology Commission of Shanghai Municipality (grant 24DX1400200), the Top-notch Project of Shanghai Oriental Talents Program (grant BJJY2025100), and the Program of Introducing Talents of Discipline to Universities (grant B16017).

语种：英文

外文关键词：Activation analysis - Bond strength (chemical) - Covalent bonds - Electrochemical electrodes - Electron transitions - Free radical reactions - Gold - Gold compounds - Molecules - Reaction kinetics - Single electron transistors

摘要：Achieving selective C-H bond activation under mild, sustainable conditions remains a major challenge. An externally applied bias provides a reagent-free driving force for promoting bond transformations, yet ensemble-averaged measurements often obscure transient intermediates and mask the intrinsic reactivity of individual chemical bonds. Here, we employ in situ scanning tunnelling microscopy break-junction (STM-BJ) measurements to directly interrogate electrocatalytic benzylic C-H activation at the single-molecule level, revealing the formation of highly conductive Au-C covalent junctions. Complementary theoretical calculations, electrochemical analyses, and radical trapping experiments indicate that the Au-C bond formation proceeds via a single-electron transfer (SET) mediated cleavage of the benzylic C-H bond, ultimately resulting in covalent coupling to the gold electrode. This strategy enables the direct transformation of nominally inert C-H bonds into robust Au-C junctions under mild conditions, while simultaneously capturing the associated bond-forming dynamics with single-bond resolution. These findings establish a mechanistic framework for bias-driven benzylic C-H activation and advance C-H functionalization toward atomically precise electrochemical manipulation of molecular transformations.