Syntheses of three-dimensional catenanes under kinetic control

Yong Wu; Qing Hui Guo; Yunyan Qiu; Jacob A. Weber; Ryan M. Young; Laura Bancroft; Yang Jiao; Hongliang Chen; Bo Song; Wenqi Liu; Yuanning Feng; Xingang Zhao; Xuesong Li; Long Zhang; Xiao Yang Chen; Hao Li; Michael R. Wasielewski; J. Fraser Stoddart

doi:10.1073/pnas.2118573119

Syntheses of three-dimensional catenanes under kinetic control

Yong Wu, Qing Hui Guo^*, Yunyan Qiu, Jacob A. Weber, Ryan M. Young, Laura Bancroft, Yang Jiao, Hongliang Chen, Bo Song, Wenqi Liu, Yuanning Feng, Xingang Zhao, Xuesong Li, Long Zhang, Xiao Yang Chen, Hao Li, Michael R. Wasielewski, J. Fraser Stoddart^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

14 Scopus citations

Abstract

Although catenanes comprising two ring-shaped components can be made in large quantities by templation, the preparation of three-dimensional (3D) catenanes with cage-shaped components is still in its infancy. Here, we report the design and syntheses of two 3D catenanes by a sequence of S_N2 reactions in one pot. The resulting triply mechanically interlocked molecules were fully characterized in both the solution and solid states. Mechanistic studies have revealed that a suit[3]ane, which contains a threefold symmetric cage component as the suit and a tribromide component as the body, is formed at elevated temperatures. This suit[3]ane was identified as the key reactive intermediate for the selective formation of the two 3D catenanes which do not represent thermodynamic minima. We foresee a future in which this particular synthetic strategy guides the rational design and production of mechanically interlocked molecules under kinetic control.

Original language	English (US)
Article number	e2118573119
Journal	Proceedings of the National Academy of Sciences of the United States of America
Volume	119
Issue number	12
DOIs	https://doi.org/10.1073/pnas.2118573119
State	Published - Mar 22 2022

Funding

ACKNOWLEDGMENTS. Financial support from Northwestern University (NU) is gratefully acknowledged. This work was supported by the National Science Foundation (DMR-2003739 to M.R.W.) and the Starry Night Science Fund of Zhejiang University Shanghai Institute for Advanced Study (SN-ZJU-SIAS-006 to H.L., Q.-H.G., and H.C.). Q.-H.G. and H.C. thank ZJU-Hangzhou Global Scientific and Technological Innovation Center for generous startup funding. Q.-H.G. thanks the National Natural Science Foundation of China (22193020 and 22193022). This work made use of the IMSERC at NU, which receives support from the National Institutes of Health (1S10OD012016-01/1S10RR019071-01A1), Soft and Hybrid Nanotechnology Experimental Resource (NSF ECCS-1542205), the state of Illinois, and the International Institute for Nanotechnology. We thank Dr. Yang Yu at NU for assistance in HPLC experiments. Financial support from Northwestern University (NU) is gratefully acknowledged. This work was supported by the National Science Foundation (DMR-2003739 to M.R.W.) and the Starry Night Science Fund of Zhejiang University Shanghai Institute for Advanced Study (SN-ZJU-SIAS-006 to H.L., Q.-H.G., and H.C.). Q.-H.G. and H.C. thank ZJU-Hangzhou Global Scientific and Technological Innovation Center for generous startup funding. Q.-H.G. thanks the National Natural Science Foundation of China (22193020 and 22193022). This work made use of the IMSERC at NU, which receives support from the National Institutes of Health (1S10OD012016-01/1S10RR019071-01A1), Soft and Hybrid Nanotechnology Experimental Resource (NSF ECCS-1542205), the state of Illinois, and the International Institute for Nanotechnology. We thank Dr. Yang Yu at NU for assistance in HPLC experiments.

Keywords

Cationic cages
Mechanically interlocked molecules
Nontrivial topologies
Suitanes
Triple [π...π] interactions

ASJC Scopus subject areas

General

Access to Document

10.1073/pnas.2118573119

Cite this

Wu, Y., Guo, Q. H., Qiu, Y., Weber, J. A., Young, R. M., Bancroft, L., Jiao, Y., Chen, H., Song, B., Liu, W., Feng, Y., Zhao, X., Li, X., Zhang, L., Chen, X. Y., Li, H., Wasielewski, M. R., & Stoddart, J. F. (2022). Syntheses of three-dimensional catenanes under kinetic control. Proceedings of the National Academy of Sciences of the United States of America, 119(12), Article e2118573119. https://doi.org/10.1073/pnas.2118573119

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abstract = "Although catenanes comprising two ring-shaped components can be made in large quantities by templation, the preparation of three-dimensional (3D) catenanes with cage-shaped components is still in its infancy. Here, we report the design and syntheses of two 3D catenanes by a sequence of SN2 reactions in one pot. The resulting triply mechanically interlocked molecules were fully characterized in both the solution and solid states. Mechanistic studies have revealed that a suit[3]ane, which contains a threefold symmetric cage component as the suit and a tribromide component as the body, is formed at elevated temperatures. This suit[3]ane was identified as the key reactive intermediate for the selective formation of the two 3D catenanes which do not represent thermodynamic minima. We foresee a future in which this particular synthetic strategy guides the rational design and production of mechanically interlocked molecules under kinetic control.",

keywords = "Cationic cages, Mechanically interlocked molecules, Nontrivial topologies, Suitanes, Triple [π...π] interactions",

author = "Yong Wu and Guo, {Qing Hui} and Yunyan Qiu and Weber, {Jacob A.} and Young, {Ryan M.} and Laura Bancroft and Yang Jiao and Hongliang Chen and Bo Song and Wenqi Liu and Yuanning Feng and Xingang Zhao and Xuesong Li and Long Zhang and Chen, {Xiao Yang} and Hao Li and Wasielewski, {Michael R.} and Stoddart, {J. Fraser}",

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Wu, Y, Guo, QH, Qiu, Y, Weber, JA, Young, RM, Bancroft, L, Jiao, Y, Chen, H, Song, B, Liu, W, Feng, Y, Zhao, X, Li, X, Zhang, L, Chen, XY, Li, H, Wasielewski, MR & Stoddart, JF 2022, 'Syntheses of three-dimensional catenanes under kinetic control', Proceedings of the National Academy of Sciences of the United States of America, vol. 119, no. 12, e2118573119. https://doi.org/10.1073/pnas.2118573119

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AU - Guo, Qing Hui

AU - Qiu, Yunyan

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AU - Jiao, Yang

AU - Chen, Hongliang

AU - Song, Bo

AU - Liu, Wenqi

AU - Feng, Yuanning

AU - Zhao, Xingang

AU - Li, Xuesong

AU - Zhang, Long

AU - Chen, Xiao Yang

AU - Li, Hao

AU - Wasielewski, Michael R.

AU - Stoddart, J. Fraser

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N2 - Although catenanes comprising two ring-shaped components can be made in large quantities by templation, the preparation of three-dimensional (3D) catenanes with cage-shaped components is still in its infancy. Here, we report the design and syntheses of two 3D catenanes by a sequence of SN2 reactions in one pot. The resulting triply mechanically interlocked molecules were fully characterized in both the solution and solid states. Mechanistic studies have revealed that a suit[3]ane, which contains a threefold symmetric cage component as the suit and a tribromide component as the body, is formed at elevated temperatures. This suit[3]ane was identified as the key reactive intermediate for the selective formation of the two 3D catenanes which do not represent thermodynamic minima. We foresee a future in which this particular synthetic strategy guides the rational design and production of mechanically interlocked molecules under kinetic control.

AB - Although catenanes comprising two ring-shaped components can be made in large quantities by templation, the preparation of three-dimensional (3D) catenanes with cage-shaped components is still in its infancy. Here, we report the design and syntheses of two 3D catenanes by a sequence of SN2 reactions in one pot. The resulting triply mechanically interlocked molecules were fully characterized in both the solution and solid states. Mechanistic studies have revealed that a suit[3]ane, which contains a threefold symmetric cage component as the suit and a tribromide component as the body, is formed at elevated temperatures. This suit[3]ane was identified as the key reactive intermediate for the selective formation of the two 3D catenanes which do not represent thermodynamic minima. We foresee a future in which this particular synthetic strategy guides the rational design and production of mechanically interlocked molecules under kinetic control.

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Syntheses of three-dimensional catenanes under kinetic control

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CCDC 2114508: Experimental Crystal Structure Determination

CCDC 2114509: Experimental Crystal Structure Determination

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Syntheses of three-dimensional catenanes under kinetic control

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CCDC 2114508: Experimental Crystal Structure Determination

CCDC 2114509: Experimental Crystal Structure Determination

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