CaltechAUTHORS
  A Caltech Library Service

Electron-catalysed molecular recognition

Jiao, Yang and Qiu, Yunyan and Zhang, Long and Liu, Wei-Guang and Mao, Haochuan and Chen, Hongliang and Feng, Yuanning and Cai, Kang and Shen, Dengke and Song, Bo and Chen, Xiao-Yang and Li, Xuesong and Zhao, Xingang and Young, Ryan M. and Stern, Charlotte L. and Wasielewski, Michael R. and Astumian, R. Dean and Goddard, William A., III and Stoddart, J. Fraser (2022) Electron-catalysed molecular recognition. Nature, 603 (7900). pp. 265-270. ISSN 0028-0836. doi:10.1038/s41586-021-04377-3. https://resolver.caltech.edu/CaltechAUTHORS:20220309-982127000

[img]
Preview
Image (JPEG) (Extended Data Fig. 1: The electron as an efficient catalyst for both covalent reactions and molecular recognition) - Supplemental Material
See Usage Policy.

190kB
[img] PDF (Supplementary Figs. 1–45, Schemes 1–9, Tables 1–8, supplementary text and notes, extensive experimental data, quantum mechanical calculation results and detailed discussions) - Supplemental Material
See Usage Policy.

27MB
[img] Crystallographic Info File (CIF) (crystallographic data for the [2]catenane in its bisradical dicationic state. CCDC 2125118) - Supplemental Material
See Usage Policy.

1MB
[img] PDF (Peer Review File) - Supplemental Material
See Usage Policy.

1MB

Use this Persistent URL to link to this item: https://resolver.caltech.edu/CaltechAUTHORS:20220309-982127000

Abstract

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.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1038/s41586-021-04377-3DOIArticle
https://rdcu.be/cIDlIPublisherFree ReadCube access
ORCID:
AuthorORCID
Qiu, Yunyan0000-0001-9279-4714
Zhang, Long0000-0002-4631-158X
Liu, Wei-Guang0000-0002-6633-7795
Feng, Yuanning0000-0002-8832-0767
Cai, Kang0000-0002-8883-0142
Song, Bo0000-0002-4337-848X
Chen, Xiao-Yang0000-0003-3449-4136
Stern, Charlotte L.0000-0002-9491-289X
Wasielewski, Michael R.0000-0003-2920-5440
Astumian, R. Dean0000-0001-7472-187X
Goddard, William A., III0000-0003-0097-5716
Stoddart, J. Fraser0000-0003-3161-3697
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.
Funders:
Funding AgencyGrant Number
Northwestern UniversityUNSPECIFIED
NSFCBET-2005250
Department of Energy (DOE)DE-FG02-99ER14999
Natural Science Foundation of Anhui Province2108085MB31
Other Numbering System:
Other Numbering System NameOther Numbering System ID
WAG1512
Issue or Number:7900
DOI:10.1038/s41586-021-04377-3
Record Number:CaltechAUTHORS:20220309-982127000
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20220309-982127000
Official Citation:Jiao, Y., Qiu, Y., Zhang, L. et al. Electron-catalysed molecular recognition. Nature 603, 265–270 (2022). https://doi.org/10.1038/s41586-021-04377-3
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:113811
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:09 Mar 2022 22:38
Last Modified:23 Apr 2022 05:13

Repository Staff Only: item control page