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  • Review Article
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Controlling dynamics in extended molecular frameworks

Nature Reviews Chemistry volume 6, pages 705–725 (2022)Cite this article

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Abstract

Molecular machines are essential dynamic components for fuel production, cargo delivery, information storage and processing in living systems. Scientists have demonstrated that they can design and synthesize artificial molecular machines that operate efficiently in isolation — for example, at high dilution in solution — fuelled by chemicals, electricity or light. To organize the spatial arrangement and motion of these machines within close proximity to one another in solid frameworks, such that useful macroscopic work can be performed, remains a challenge in both chemical and materials science. In this Review, we summarize the progress that has been made during the past decade in organizing dynamic molecular entities in such solid frameworks. Emerging applications of these dynamic smart materials in the contexts of molecular recognition, optoelectronics, drug delivery, photodynamic therapy and water desalination are highlighted. Finally, we review recent work on a new non-equilibrium adsorption phenomenon for which we have coined the term mechanisorption. The ability to use external energy to drive directional processes in mechanized extended frameworks augurs well for the future development of artificial molecular factories.

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Fig. 1: A Venn diagram showing the properties of metal–organic frameworks (MOFs) that render23 them an excellent platform for accommodating dynamic components.
Fig. 2: Chronology associated with the advances in robust dynamics23 from 2008 to the present day.
Fig. 3: Summary of non-directional rotational movements observed in molecular turnstiles.
Fig. 4: Summary of possible non-directional motions observed in mechanically interlocked molecules incorporated in extended molecular frameworks.
Fig. 5: Structural representations of switchable configurations of azobenzenes and switchable constitutions in diarylethenes and spiropyrans in struts of extended molecular frameworks.
Fig. 6: Graphical representations of controlled switchable motions using dative bonds in mechanically interlocked molecules (MIMs).
Fig. 7: Graphical illustration of continuous unidirectional motion of rotary motors in MOFs.
Fig. 8: Graphical illustration of continuous unidirectional motion of linear motors (pumps) in MOFs.
Fig. 9: Sequential pumping of different rings onto surfaces.
Fig. 10: Scope of mechanisorption and its potential application.
Fig. 11: Outlook for robust dynamics.

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Acknowledgements

The authors acknowledge Northwestern University for financial support. The authors thank Y. Qiu, J. Seale and K.-Y. Wang for their helpful discussions of some of the topics covered in this manuscript.

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Authors and Affiliations

  1. Department of Chemistry, Northwestern University, Evanston, IL, USA

    Liang Feng & J. Fraser Stoddart

  2. Department of Physics and Astronomy, University of Maine, Orono, ME, USA

    R. Dean Astumian

  3. School of Chemistry, University of New South Wales, Sydney, New South Wales, Australia

    J. Fraser Stoddart

  4. Stoddart Institute of Molecular Science, Department of Chemistry, Zhejiang University, Hangzhou, China

    J. Fraser Stoddart

  5. ZJU-Hangzhou Global Scientific and Technological Innovation Center, Hangzhou, China

    J. Fraser Stoddart

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Feng, L., Astumian, R.D. & Stoddart, J.F. Controlling dynamics in extended molecular frameworks. Nat Rev Chem 6, 705–725 (2022). https://doi.org/10.1038/s41570-022-00412-7

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