Precise electrical gating of the single-molecule Mizoroki-Heck reaction

Lei Zhang; Chen Yang; Chenxi Lu; Xingxing Li; Yilin Guo; Jianning Zhang; Jinglong Lin; Zhizhou Li; Chuancheng Jia; Jinlong Yang; K N Houk; Fanyang Mo; Xuefeng Guo

doi:10.1038/s41467-022-32351-8

Precise electrical gating of the single-molecule Mizoroki-Heck reaction

Nat Commun. 2022 Aug 5;13(1):4552. doi: 10.1038/s41467-022-32351-8.

Authors

Lei Zhang^#^{1

2}, Chen Yang^#¹, Chenxi Lu^#³, Xingxing Li⁴, Yilin Guo¹, Jianning Zhang², Jinglong Lin², Zhizhou Li¹, Chuancheng Jia⁵, Jinlong Yang⁴, K N Houk⁶, Fanyang Mo⁷, Xuefeng Guo^{8

9}

Affiliations

¹ Beijing National Laboratory for Molecular Sciences, National Biomedical Imaging Centre, College of Chemistry and Molecular Engineering, Peking University, 292 Chengfu Road, Haidian District, Beijing, 100871, P. R. China.
² School of Materials Science and Engineering, Peking University, Beijing, 100871, P. R. China.
³ Department of Chemistry and Biochemistry, University of California, Los Angeles, CA, 90095, USA.
⁴ Hefei National Laboratory for Physical Sciences at Microscale, University of Science and Technology of China, Anhui, 230026, P. R. China.
⁵ Centre of Single-Molecule Sciences, Institute of Modern Optics, Frontiers Science Centre for New Organic Matter, College of Electronic Information and Optical Engineering, Nankai University, 38 Tongyan Road, Jinnan District, Tianjin, 300350, P. R. China.
⁶ Department of Chemistry and Biochemistry, University of California, Los Angeles, CA, 90095, USA. houk@chem.ucla.edu.
⁷ School of Materials Science and Engineering, Peking University, Beijing, 100871, P. R. China. fmo@pku.edu.cn.
⁸ Beijing National Laboratory for Molecular Sciences, National Biomedical Imaging Centre, College of Chemistry and Molecular Engineering, Peking University, 292 Chengfu Road, Haidian District, Beijing, 100871, P. R. China. guoxf@pku.edu.cn.
⁹ Centre of Single-Molecule Sciences, Institute of Modern Optics, Frontiers Science Centre for New Organic Matter, College of Electronic Information and Optical Engineering, Nankai University, 38 Tongyan Road, Jinnan District, Tianjin, 300350, P. R. China. guoxf@pku.edu.cn.

^# Contributed equally.

Abstract

Precise tuning of chemical reactions with predictable and controllable manners, an ultimate goal chemists desire to achieve, is valuable in the scientific community. This tunability is necessary to understand and regulate chemical transformations at both macroscopic and single-molecule levels to meet demands in potential application scenarios. Herein, we realise accurate tuning of a single-molecule Mizoroki-Heck reaction via applying gate voltages as well as complete deciphering of its detailed intrinsic mechanism by employing an in-situ electrical single-molecule detection, which possesses the capability of single-event tracking. The Mizoroki-Heck reaction can be regulated in different dimensions with a constant catalyst molecule, including the molecular orbital gating of Pd(0) catalyst, the on/off switching of the Mizoroki-Heck reaction, the promotion of its turnover frequency, and the regulation of each elementary reaction within the Mizoroki-Heck catalytic cycle. These results extend the tuning scope of chemical reactions from the macroscopic view to the single-molecule approach, inspiring new insights into designing different strategies or devices to unveil reaction mechanisms and discover novel phenomena.

Grants and funding

22150013, 21727806, 21933001, 21772003 and 22071004/National Natural Science Foundation of China (National Science Foundation of China)