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Article

Tuning Single-Molecule Conductance by Controlled Electric Field-Induced trans-to-cis Isomerisation

1
Department of Chemistry, Federal University of São Carlos, São Carlos 13565-905, Brazil
2
Max Planck Institute for Polymer Research, Ackermannweg 10, 55128 Mainz, Germany
3
Departamento de Química de los Materiales, Facultad de Química y Biología, Universidad de Santiago de Chile, Casilla 40, Correo 33, Santiago 9170022, Chile
4
Department of Chemistry, Myongji University, Myongji-Ro 116, Cheoin-Gu, Yongin 17058, Gyeonggi-Do, Korea
5
Department of Chemistry, Faculty of Natural & Mathematical Sciences, King’s College London Britannia House, 7 Trinity Street, London SE1 1DB, UK
*
Authors to whom correspondence should be addressed.
Current address: Max Planck Institute for Polymer Research, Ackermannweg 10, 55128 Mainz, Germany.
Academic Editor: Linda Angela Zotti
Appl. Sci. 2021, 11(8), 3317; https://doi.org/10.3390/app11083317
Received: 13 March 2021 / Revised: 3 April 2021 / Accepted: 5 April 2021 / Published: 7 April 2021
(This article belongs to the Special Issue Molecular Electronics)
External electric fields (EEFs) have proven to be very efficient in catalysing chemical reactions, even those inaccessible via wet-chemical synthesis. At the single-molecule level, oriented EEFs have been successfully used to promote in situ single-molecule reactions in the absence of chemical catalysts. Here, we elucidate the effect of an EEFs on the structure and conductance of a molecular junction. Employing scanning tunnelling microscopy break junction (STM-BJ) experiments, we form and electrically characterize single-molecule junctions of two tetramethyl carotene isomers. Two discrete conductance signatures show up more prominently at low and high applied voltages which are univocally ascribed to the trans and cis isomers of the carotenoid, respectively. The difference in conductance between both cis-/trans- isomers is in concordance with previous predictions considering π-quantum interference due to the presence of a single gauche defect in the trans isomer. Electronic structure calculations suggest that the electric field polarizes the molecule and mixes the excited states. The mixed states have a (spectroscopically) allowed transition and, therefore, can both promote the cis-isomerization of the molecule and participate in electron transport. Our work opens new routes for the in situ control of isomerisation reactions in single-molecule contacts. View Full-Text
Keywords: molecular electronics; single-molecule junctions; STM break-junction; in-situ isomerisation; carotenoids molecular electronics; single-molecule junctions; STM break-junction; in-situ isomerisation; carotenoids
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MDPI and ACS Style

Quintans, C.S.; Andrienko, D.; Domke, K.F.; Aravena, D.; Koo, S.; Díez-Pérez, I.; Aragonès, A.C. Tuning Single-Molecule Conductance by Controlled Electric Field-Induced trans-to-cis Isomerisation. Appl. Sci. 2021, 11, 3317. https://doi.org/10.3390/app11083317

AMA Style

Quintans CS, Andrienko D, Domke KF, Aravena D, Koo S, Díez-Pérez I, Aragonès AC. Tuning Single-Molecule Conductance by Controlled Electric Field-Induced trans-to-cis Isomerisation. Applied Sciences. 2021; 11(8):3317. https://doi.org/10.3390/app11083317

Chicago/Turabian Style

Quintans, C.S., Denis Andrienko, Katrin F. Domke, Daniel Aravena, Sangho Koo, Ismael Díez-Pérez, and Albert C. Aragonès 2021. "Tuning Single-Molecule Conductance by Controlled Electric Field-Induced trans-to-cis Isomerisation" Applied Sciences 11, no. 8: 3317. https://doi.org/10.3390/app11083317

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