The solid state is typically not well suited to sustaining fast molecular motion, but in recent years a variety of molecular machines, switches and rotors have been successfully engineered within porous crystals and on surfaces. Here we show a fast-rotating molecular rotor within the bicyclopentane–dicarboxylate struts of a zinc-based metal–organic framework—the carboxylate groups anchored to the metal clusters act as an axle while the bicyclic unit is free to rotate. The three-fold bipyramidal symmetry of the rotator conflicts with the four-fold symmetry of the struts within the cubic crystal cell of the zinc metal–organic framework. This frustrates the formation of stable conformations, allowing for the continuous, unidirectional, hyperfast rotation of the bicyclic units with an energy barrier of 6.2 cal mol−1 and a high frequency persistent for several turns even at very low temperatures (1010 Hz below 2 K). Using zirconium instead of zinc led to a different metal cluster–carboxylate coordination arrangement in the resulting metal–organic framework, and much slower rotation of the bicyclic units.
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X-ray crystallographic data have been deposited at the Cambridge Crystallographic Data Centre (http://www.ccdc.cam.ac.uk/) with reference numbers CCDC 1994502 (single-crystal Zn-FTR), 1994503 (Zn-FTR refined from PXRD) and 1994504 (Zr-FTR refined from PXRD). A copy of the data can be obtained free of charge via https://www.ccdc.cam.ac.uk/structures/. All other data supporting the findings of this study are available within the article and its Supplementary Information. Data are also available from the corresponding author upon reasonable request. Raw data are available for Fig. 5. Source data are provided with this paper.
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Financial support from the Italian Ministry of University and Research (MIUR) through the grant ‘Dipartimenti di Eccellenza-2017 Materials For Energy’ is acknowledged. This research was funded by the PRIN-2015CTEBBA-003 and PRIN-20173L7W8K grants. I. Supino is acknowledged for her help during sample preparation.
The authors declare no competing interests.
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Methods for solid-state NMR spectroscopy measurements. Characterization of Zn-FTR and Zr-FTR MOFs (TGA, SEM, IR, gas adsorption, PXRD and single-crystal diffraction measurement and solid-state NMR). Additional details on rotor dynamics (solid-state NMR data, muon spin relaxation measurements and molecular dynamics simulations). Supplementary Figs. 1–49 and Tables 1–15.
CIF for Zn-FTR (CCDC reference 1994502).
Structure factors for Zn-FTR (CCDC reference 1994502).
CIF for Zn-FTR refined from XRPD (CCDC reference 1994503).
CIF for Zr-FTR refined from XRPD (CCDC reference 1994504).
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Perego, J., Bracco, S., Negroni, M. et al. Fast motion of molecular rotors in metal–organic framework struts at very low temperatures. Nat. Chem. 12, 845–851 (2020). https://doi.org/10.1038/s41557-020-0495-3