Abstract
Investigating how electrons propagate through a single molecule is one of the missions of molecular electronics. Electrons, however, are also efficient catalysts for conducting radical reactions, a property that is often overlooked by chemists. Special attention should be paid to electron catalysis when interpreting single-molecule conductance results for the simple reason that an unexpected reaction mediated or triggered by electrons might take place in the single-molecule junction. Here, we describe a counterintuitive structure-property relationship that molecules, both linear and cyclic, employing a saturated bipyridinium-ethane backbone, display a similar conductance signature when compared to junctions formed with molecules containing conjugated bipyridinium-ethene backbones. We describe an ethane-to-ethene transformation, which proceeds in the single-molecule junction by an electron-catalyzed dehydrogenation. Electrochemically based ensemble experiments and theoretical calculations have revealed that the electrons trigger the redox process, and the electric field promotes the dehydrogenation. This finding not only demonstrates the importance of electron catalysis when interpreting experimental results, but also charts a pathway to gaining more insight into the mechanism of electrocatalytic hydrogen production at the single-molecule level.
Original language | English (US) |
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Pages (from-to) | 8476-8487 |
Number of pages | 12 |
Journal | Journal of the American Chemical Society |
Volume | 143 |
Issue number | 22 |
DOIs | |
State | Published - Jun 9 2021 |
Funding
The authors would like to thank Northwestern University for its continued support of this research. This work was supported by the U.S. Department of Energy, Office of Science, Office of Basic Eneregy Sciences under Award DE-FG02-99ER14999 (M.R.W.). The authors acknowledge the Integrated Molecular Structure Education and Research Center (IMSERC) at NU for providing access to equipment for the experiments. The research conducted at Xiamen University was supported by the National Key R&D Program of China (2017YFA0204902) and the National Natural Science Foundation of China (Grants 21673195 and 21722305). Computational investigations by H.G. were supported by the Natural Sciences and Engineering Research Council of Canada. The authors thank the High Performance Computing Centre of McGill University, CalcuQuebec, and Compute Canada for computation facilities which made the simulations possible. The authors would like to thank Northwestern University for its continued support of this research. This work was supported by the U.S. Department of Energy, Office of Science, Office of Basic Eneregy Sciences under Award DE-FG02-99ER14999 (M.R.W.). The authors acknowledge the Integrated Molecular Structure Education and Research Center (IMSERC) at NU for providing access to equipment for the experiments. The research conducted at Xiamen University was supported by the National Key R&D Program of China (2017YFA0204902) and the National Natural Science Foundation of China (Grants 21673195 and 21722305). Computational investigations by H.G. were supported by the Natural Sciences and Engineering Research Council of Canada. The authors thank the High Performance Computing Centre of McGill University, CalcuQuebec and Compute Canada for computation facilities which made the simulations possible.
ASJC Scopus subject areas
- General Chemistry
- Biochemistry
- Catalysis
- Colloid and Surface Chemistry
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CCDC 2035269: Experimental Crystal Structure Determination
Chen, H. (Contributor), Jiang, F. (Contributor), Hu, C. (Contributor), Jiao, Y. (Contributor), Chen, S. (Contributor), Qiu, Y. (Contributor), Zhou, P. (Contributor), Zhang, L. (Contributor), Cai, K. (Contributor), Song, B. (Contributor), Chen, X.-Y. (Contributor), Zhao, X. (Contributor), Wasielewski, M. R. (Contributor), Guo, H. (Contributor), Hong, W. (Contributor) & Stoddart, J. F. (Contributor), Cambridge Crystallographic Data Centre, 2021
DOI: 10.5517/ccdc.csd.cc269vv7, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc269vv7&sid=DataCite
Dataset
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CCDC 2035270: Experimental Crystal Structure Determination
Chen, H. (Contributor), Jiang, F. (Contributor), Hu, C. (Contributor), Jiao, Y. (Contributor), Chen, S. (Contributor), Qiu, Y. (Contributor), Zhou, P. (Contributor), Zhang, L. (Contributor), Cai, K. (Contributor), Song, B. (Contributor), Chen, X.-Y. (Contributor), Zhao, X. (Contributor), Wasielewski, M. R. (Contributor), Guo, H. (Contributor), Hong, W. (Contributor) & Stoddart, J. F. (Contributor), Cambridge Crystallographic Data Centre, 2021
DOI: 10.5517/ccdc.csd.cc269vw8, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc269vw8&sid=DataCite
Dataset
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CCDC 2035271: Experimental Crystal Structure Determination
Chen, H. (Contributor), Jiang, F. (Contributor), Hu, C. (Contributor), Jiao, Y. (Contributor), Chen, S. (Contributor), Qiu, Y. (Contributor), Zhou, P. (Contributor), Zhang, L. (Contributor), Cai, K. (Contributor), Song, B. (Contributor), Chen, X.-Y. (Contributor), Zhao, X. (Contributor), Wasielewski, M. R. (Contributor), Guo, H. (Contributor), Hong, W. (Contributor) & Stoddart, J. F. (Contributor), Cambridge Crystallographic Data Centre, 2021
DOI: 10.5517/ccdc.csd.cc269vx9, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc269vx9&sid=DataCite
Dataset