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      Voltage-driven control of single-molecule keto-enol equilibrium in a two-terminal junction system

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          Abstract

          Keto-enol tautomerism, describing an equilibrium involving two tautomers with distinctive structures, provides a promising platform for modulating nanoscale charge transport. However, such equilibria are generally dominated by the keto form, while a high isomerization barrier limits the transformation to the enol form, suggesting a considerable challenge to control the tautomerism. Here, we achieve single-molecule control of a keto-enol equilibrium at room temperature by using a strategy that combines redox control and electric field modulation. Based on the control of charge injection in the single-molecule junction, we could access charged potential energy surfaces with opposite thermodynamic driving forces, i.e., exhibiting a preference for the conducting enol form, while the isomerization barrier is also significantly reduced. Thus, we could selectively obtain desired and stable tautomers, which leads to significant modulation of the single-molecule conductance. This work highlights the concept of single-molecule control of chemical reactions on more than one potential energy surface.

          Abstract

          Keto-enol tautomerism offers a promising platform for modulating charge transport at the nanoscale. Here, the authors show that the keto-enol equilibrium can be modulated on the single-molecule scale by controlling charge injection in a two-terminal junction system.

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          Most cited references47

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          Electron transfers in chemistry and biology

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            Measurement of single-molecule resistance by repeated formation of molecular junctions.

            The conductance of a single molecule connected to two gold electrodes was determined by repeatedly forming thousands of gold-molecule-gold junctions. Conductance histograms revealed well-defined peaks at integer multiples of a fundamental conductance value, which was used to identify the conductance of a single molecule. The resistances near zero bias were 10.5 +/- 0.5, 51 +/- 5, 630 +/- 50, and 1.3 +/- 0.1 megohms for hexanedithiol, octanedithiol, decanedithiol, and 4,4' bipyridine, respectively. The tunneling decay constant (betaN) for N-alkanedithiols was 1.0 +/- 0.1 per carbon atom and was weakly dependent on the applied bias. The resistance and betaN values are consistent with first-principles calculations.
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              Electrostatic catalysis of a Diels-Alder reaction.

              It is often thought that the ability to control reaction rates with an applied electrical potential gradient is unique to redox systems. However, recent theoretical studies suggest that oriented electric fields could affect the outcomes of a range of chemical reactions, regardless of whether a redox system is involved. This possibility arises because many formally covalent species can be stabilized via minor charge-separated resonance contributors. When an applied electric field is aligned in such a way as to electrostatically stabilize one of these minor forms, the degree of resonance increases, resulting in the overall stabilization of the molecule or transition state. This means that it should be possible to manipulate the kinetics and thermodynamics of non-redox processes using an external electric field, as long as the orientation of the approaching reactants with respect to the field stimulus can be controlled. Here, we provide experimental evidence that the formation of carbon-carbon bonds is accelerated by an electric field. We have designed a surface model system to probe the Diels-Alder reaction, and coupled it with a scanning tunnelling microscopy break-junction approach. This technique, performed at the single-molecule level, is perfectly suited to deliver an electric-field stimulus across approaching reactants. We find a fivefold increase in the frequency of formation of single-molecule junctions, resulting from the reaction that occurs when the electric field is present and aligned so as to favour electron flow from the dienophile to the diene. Our results are qualitatively consistent with those predicted by quantum-chemical calculations in a theoretical model of this system, and herald a new approach to chemical catalysis.
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                Author and article information

                Contributors
                sason@yfaat.ch.huji.ac.il
                xiahp@sustech.edu.cn
                whong@xmu.edu.cn
                Journal
                Nat Commun
                Nat Commun
                Nature Communications
                Nature Publishing Group UK (London )
                2041-1723
                20 June 2023
                20 June 2023
                2023
                : 14
                : 3657
                Affiliations
                [1 ]GRID grid.12955.3a, ISNI 0000 0001 2264 7233, State Key Laboratory of Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, , Xiamen University, ; Xiamen, 361005 P. R. China
                [2 ]GRID grid.263817.9, ISNI 0000 0004 1773 1790, Shenzhen Grubbs Institute, Department of Chemistry, , Southern University of Science and Technology, ; Shenzhen, 518055 P. R. China
                [3 ]GRID grid.9619.7, ISNI 0000 0004 1937 0538, Institute of Chemistry, , Edmond J. Safra Campus at Givat Ram, The Hebrew University, ; Jerusalem, 91904 Israel
                [4 ]GRID grid.4444.0, ISNI 0000 0001 2112 9282, Ecole Nationale Supérieure de Chimie de Paris, Université PSL, CNRS, Institute of Chemistry for Life and Health Sciences, ; 75 005 Paris, France
                Author information
                http://orcid.org/0000-0001-7555-8250
                http://orcid.org/0000-0002-7252-1900
                http://orcid.org/0000-0002-0545-2896
                http://orcid.org/0000-0001-8437-2677
                http://orcid.org/0000-0001-7643-9421
                http://orcid.org/0000-0002-2688-6634
                http://orcid.org/0000-0003-4080-6175
                Article
                39198
                10.1038/s41467-023-39198-7
                10281950
                37339947
                9bfeda7d-c3ea-4e00-a8ab-13478ddfc6b0
                © The Author(s) 2023

                Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/.

                History
                : 16 January 2023
                : 30 May 2023
                Funding
                Funded by: FundRef https://doi.org/10.13039/501100001809, National Natural Science Foundation of China (National Science Foundation of China);
                Award ID: 21722305
                Award Recipient :
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                © Springer Nature Limited 2023

                Uncategorized
                electronic materials,molecular electronics,electronic properties and materials

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