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Published March 10, 2022 | Supplemental Material
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Electron-catalysed molecular recognition


Molecular recognition and supramolecular assembly cover a broad spectrum of non-covalently orchestrated phenomena between molecules. Catalysis of such processes, however, unlike that for the formation of covalent bonds, is limited to approaches that rely on sophisticated catalyst design. Here we establish a simple and versatile strategy to facilitate molecular recognition by extending electron catalysis, which is widely applied in synthetic covalent chemistry, into the realm of supramolecular non-covalent chemistry. As a proof of principle, we show that the formation of a trisradical complex22 between a macrocyclic host and a dumbbell-shaped guest—a molecular recognition process that is kinetically forbidden under ambient conditions—can be accelerated substantially on the addition of catalytic amounts of a chemical electron source. It is, therefore, electrochemically possible to control the molecular recognition temporally and produce a nearly arbitrary molar ratio between the substrates and complexes ranging between zero and the equilibrium value. Such kinetically stable supramolecular systems are difficult to obtain precisely by other means. The use of the electron as a catalyst in molecular recognition will inspire chemists and biologists to explore strategies that can be used to fine-tune non-covalent events, control assembly at different length scales and ultimately create new forms of complex matter.

Additional Information

© The Author(s), under exclusive licence to Springer Nature Limited 2022. Received 06 September 2021. Accepted 22 December 2021. Published 09 March 2022. Issue Date 10 March 2022. We thank Northwestern University (NU) for its continued support of this research and acknowledge the Integrated Molecular Structure Education and Research Center (IMSERC) at NU for providing access to equipment for relevant experiments. The computational investigations at California Institute of Technology were supported by National Science Foundation grant no. CBET-2005250 (W.-G.L. and W.A.G.). This work was also supported by the Department of Energy, Office of Science, Office of Basic Energy Sciences under Award DE-FG02-99ER14999 (M.R.W.) and the Natural Science Foundation of Anhui Province grant no. 2108085MB31 (D.S.). Contributions. Y.J., Y.Q. and J.F.S. conceived the idea for this project. L.Z. proposed a key mechanistic conjecture. W.-G.L. and W.A.G. performed quantum mechanical calculations. Y.J. and Y.Q. synthesized and characterized the materials with the help of H.C., Y.F., K.C., D.S., B.S., X.-Y.C., X.L. and X.Z. H.M., R.M.Y. and M.R.W. performed the electron paramagnetic resonance characterizations and detailed analyses. C.L.S. performed the single-crystal X-ray diffraction. R.D.A. contributed to the theoretical analyses on the mechanism of electron catalysis. Y.J., Y.Q. and J.F.S. wrote the first and second drafts of the paper. J.F.S. and W.A.G. directed the project. All the authors participated in evaluating the results and commented on the manuscript. Data availability. The data that support the findings of this study are available within the paper and its Supplementary Information files. Competing interests. Y.J., Y.Q. and J.F.S. have filed a patent application lodged with Northwestern University (INVO reference no. NU 2021-248) based on this work. Peer review information. Nature thanks Robert Francke and the other, anonymous, reviewer(s) for their contribution to the peer review of this work. Peer reviewer reports are available.

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August 22, 2023
October 23, 2023