Litcius/Paper detail

Regulating enol–keto tautomerism at the single-molecule level with a confined optical field

Adila Adijiang, Yunlong Ge, Hefa Feng, Yan Yan, Xin Zuo, Haoyu Wang, Xueyan Zhao, Min Tan, Surong Zhang, Xiaona Xu, Lichuan Chen, Chuan‐Kui Wang, Zong‐Liang Li, Dong Xiang

2025Chemical Science5 citationsDOIOpen Access PDF

Abstract

monitoring of the conductance evolution of thousands of single-molecule junctions, we demonstrated that the enol → keto transformation can be significantly promoted by confined ultraviolet (UV) irradiation at an extremely low intensity (1‰ of sunshine) employing antenna electrodes. Our study reveals that the conductance of the enol form is an order of magnitude larger than that of the keto form although both have similar molecular lengths and identical anchoring groups, and the enol form shows a current rectification behaviour which is completely absent in the keto form. Supported by UV-vis measurements, wavelength-dependent conductance measurements, and theoretical calculations, the mechanism for the enol → keto transformation promoted by the gap-electrode-confined optical field was elucidated, offering a new strategy to regulate the tautomerism processes at the single molecule level, and implying a potential multi-functional application of β-diketones in the fabrication of rectifiers and synchronous switches.

Topics & Concepts

TautomerKeto–enol tautomerismEnolMoleculeField (mathematics)ChemistryStereochemistryOrganic chemistryMathematicsCatalysisPure mathematicsMolecular Junctions and NanostructuresPhotochemistry and Electron Transfer StudiesPorphyrin and Phthalocyanine Chemistry