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Fast motion of molecular rotors in metal–organic framework struts at very low temperatures

Nature Chemistry volume 12, pages 845–851 (2020)Cite this article

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Abstract

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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Fig. 1: Factors influencing the molecular rotor dynamics, conformations of the rotator and stator in the ligand and the resulting energy profiles.
Fig. 2: Crystal structure, cavity geometry and rotors in the frameworks.
Fig. 3: Crossed (Zn) and in-plane (Zr) conformations with torsional energy profiles of the ligands.
Fig. 4: Solid-state NMR spectra and 1H T1 spin–lattice relaxation times of the molecular rotor in the MOFs recorded at various magnetic fields.
Fig. 5: Molecular dynamics results for Zn-FTR calculated at various temperatures.

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Data availability

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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Acknowledgements

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.

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Authors and Affiliations

  1. Department of Materials Science, University of Milano Bicocca, Milan, Italy

    Jacopo Perego, Silvia Bracco, Mattia Negroni, Charl X. Bezuidenhout, Angiolina Comotti & Piero Sozzani

  2. Department of Physics, University of Pavia, Pavia, Italy

    Giacomo Prando & Pietro Carretta

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Contributions

A.C. and P.S. conceived the study. J.P. designed the materials synthesis and characterization. S.B., G.P., M.N., and P.C. carried out the NMR measurements and C.B., the theoretical calculations. A.C., P.S. and S.B. wrote the manuscript with suggestions from all the authors.

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Correspondence to Angiolina Comotti or Piero Sozzani.

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Supplementary information

Supplementary Information

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.

Supplementary Data 1

CIF for Zn-FTR (CCDC reference 1994502).

Supplementary Data 2

Structure factors for Zn-FTR (CCDC reference 1994502).

Supplementary Data 3

CIF for Zn-FTR refined from XRPD (CCDC reference 1994503).

Supplementary Data 4

CIF for Zr-FTR refined from XRPD (CCDC reference 1994504).

Source data

Source Data Fig. 5

Zn-FTR rotor speeds and accumulative rotor turns at 298 K and 10 K; Zn-FTR rotor rotation angle at 298 K, 10 K and 2.3 K.

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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

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