Ionic Liquid Accelerates Electrochemically Driven Single‐Molecule Oxidative Coupling

J Jiao Xun (Pen‐Tung Sah Institute of Micro‐Nano Science and Technology, State Key Laboratory of Physical Chemistry of Solid Surfaces, Xiang An Biomedicine Laboratory Xiamen University Xiamen 361005 China) J Jia‐Xin Chen (Spin‐X Institute, School of Chemistry and Chemical Engineering, Guangdong‐Hong Kong‐Macao Joint Laboratory of Optoelectronic and Magnetic Functional Materials, State Key Laboratory of Luminescent Materials and Devices South China University of Technology Guangzhou 511442 China) T Tong‐Ruo Diao (Pen‐Tung Sah Institute of Micro‐Nano Science and Technology, State Key Laboratory of Physical Chemistry of Solid Surfaces, Xiang An Biomedicine Laboratory Xiamen University Xiamen 361005 China) L Lai‐Ke Chen (Pen‐Tung Sah Institute of Micro‐Nano Science and Technology, State Key Laboratory of Physical Chemistry of Solid Surfaces, Xiang An Biomedicine Laboratory Xiamen University Xiamen 361005 China) Y Yu‐Ling Zou (Pen‐Tung Sah Institute of Micro‐Nano Science and Technology, State Key Laboratory of Physical Chemistry of Solid Surfaces, Xiang An Biomedicine Laboratory Xiamen University Xiamen 361005 China) C Chen‐Cong Luo (Pen‐Tung Sah Institute of Micro‐Nano Science and Technology, State Key Laboratory of Physical Chemistry of Solid Surfaces, Xiang An Biomedicine Laboratory Xiamen University Xiamen 361005 China) J Jia Shi (State Key Laboratory of Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering & Institute of Artificial Intelligence & Innovation Laboratory for Sciences and Technologies of Energy Materials of Fujian Province (IKKEM)) D De‐Yin Wu (State Key Laboratory of Physical Chemistry of Solid Surface College of Chemistry and Chemical Engineering Xiamen University Xiamen 361005 China) Y Yang Yang

Abstract

Abstract Molecular adsorption covers a broad spectrum of chemical processes and device fabrications at solid/liquid interfaces. The unraveling of the underlying mechanisms relies on regulating molecular adsorption. However, achieving such regulation at the single‐molecule level remains a challenge. Herein, we utilized a combined ionic liquid and scanning tunneling microscope break junction methods to tune single 4‐(pyridin‐4‐yl)aniline molecules gradually from the flat configuration to the upright one and found that only the upright configuration can trigger the oxidative coupling. Experimental and theoretical findings demonstrated that the ionic liquid reduced the electron density of the Au electrode, giving rise to the evolution of the interaction between molecule and electrode from the Au‐π dominated coupling to the Au‐σ dominated one. This work will inspire the exploration of strategies that can control the molecular assembly, accelerate the chemical reaction, and promote the fabrication of organic devices.

Article Details

Volume / Issue Vol. 64, Issue 32
Published August 04, 2025
ISSN 1433-7851
Publisher Wiley

Journal Info

Angewandte Chemie International Edition

Wiley

ISSN: 1433-7851 Physical Sciences

Authors (9)

J

Jiao Xun

Pen‐Tung Sah Institute of Micro‐Nano Science and Technology, State Key Laboratory of Physical Chemistry of Solid Surfaces, Xiang An Biomedicine Laboratory Xiamen University Xiamen 361005 China

J

Jia‐Xin Chen

Spin‐X Institute, School of Chemistry and Chemical Engineering, Guangdong‐Hong Kong‐Macao Joint Laboratory of Optoelectronic and Magnetic Functional Materials, State Key Laboratory of Luminescent Materials and Devices South China University of Technology Guangzhou 511442 China

T

Tong‐Ruo Diao

Pen‐Tung Sah Institute of Micro‐Nano Science and Technology, State Key Laboratory of Physical Chemistry of Solid Surfaces, Xiang An Biomedicine Laboratory Xiamen University Xiamen 361005 China

L

Lai‐Ke Chen

Pen‐Tung Sah Institute of Micro‐Nano Science and Technology, State Key Laboratory of Physical Chemistry of Solid Surfaces, Xiang An Biomedicine Laboratory Xiamen University Xiamen 361005 China

Y

Yu‐Ling Zou

Pen‐Tung Sah Institute of Micro‐Nano Science and Technology, State Key Laboratory of Physical Chemistry of Solid Surfaces, Xiang An Biomedicine Laboratory Xiamen University Xiamen 361005 China

C

Chen‐Cong Luo

Pen‐Tung Sah Institute of Micro‐Nano Science and Technology, State Key Laboratory of Physical Chemistry of Solid Surfaces, Xiang An Biomedicine Laboratory Xiamen University Xiamen 361005 China

J

Jia Shi

State Key Laboratory of Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering & Institute of Artificial Intelligence & Innovation Laboratory for Sciences and Technologies of Energy Materials of Fujian Province (IKKEM)

D

De‐Yin Wu

State Key Laboratory of Physical Chemistry of Solid Surface College of Chemistry and Chemical Engineering Xiamen University Xiamen 361005 China

Y

Yang Yang