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.
Saibil, H. Chaperone machines for protein folding, unfolding and disaggregation. Nat. Rev. Mol. Cell Biol. 14, 630–642 (2013).
Kinbara, K. & Aida, T. Towards intelligent molecular machines: Directed motions of biological and artificial molecules and assemblies. Chem. Rev. 105, 1377–1400 (2005).
Olesen, C. et al. The structural basis of calcium transport by the calcium pump. Nature 450, 1036–1042 (2007).
Howard, J., Hudspeth, A. J. & Vale, R. D. Movement of microtubules by single kinesin molecules. Nature 342, 154–158 (1989).
Preben Morth, J. et al. A structural overview of the plasma membrane Na+,K+-ATPase and H+-ATPase ion pumps. Nat. Rev. Mol. Cell Biol. 12, 60–70 (2011).
Vogelsberg, C. S. & Garcia-Garibay, M. A. Crystalline molecular machines: function, phase order, dimensionality, and composition. Chem. Soc. Rev. 41, 1892–1910 (2012).
Bracco, S., Comotti, A. & Sozzani, P. Molecular rotors built in porous materials. Acc. Chem. Res. 49, 1701–1710 (2016).
Danowski, W. et al. Unidirectional rotary motion in a metal-organic framework. Nat. Nanotechnol. 488, 488–494 (2019).
Deng, H., Olson, M. A., Stoddart, J. F. & Yaghi, O. M. Robust dynamics. Nat. Chem. 2, 439–443 (2010).
Zhu, K., O’Keefe, C. A., Vukotic, V. N., Schurko, R. W. & Loeb, S. J. A molecular shuttle that operates inside a metal-organic framework. Nat. Chem. 7, 514–519 (2015).
Kobr, L. et al. Inclusion compound based approach to arrays of artificial dipolar molecular rotors. A surface inclusion. J. Am. Chem. Soc. 134, 10122–10131 (2012).
Inukai, M. et al. Control of molecular rotor rotational frequencies in porous coordination polymers using a solid-solution approach. J. Am. Chem. Soc. 137, 12183–12186 (2015).
Vogelsberg, C. S. et al. Ultrafast rotation in an amphidynamic crystalline metal organic framework. Proc. Natl Acad. Sci. USA 114, 13613–13618 (2017).
Michl, J., Charles, E. & Sykes, H. Molecular rotors and motors: recent advances and future challenges. ACS Nano 3, 1042–1048 (2009).
Prokop, A., Vacek, J. & Michl, J. Friction in carborane-based molecular rotors driven by gas flow or electric field: classical molecular dynamics. ACS Nano 6, 1901–1914 (2012).
Coskun, A., Banaszak, M., Astumian, R. D., Stoddart, J. F. & Grzybowski, B. A. Great expectations: can artificial molecular machines deliver on their promise? Chem. Soc. Rev. 41, 19–30 (2012).
Steuerman, D. W. et al. Molecular-mechanical switch-based solid-state electrochromic devices. Angew. Chem. Int. Ed. 43, 6486–6491 (2004).
Collier, C. P. et al. A catenane-based solid state electronically reconfigurable switch. Science 289, 1172–1175 (2000).
Kaleta, J. et al. Surface inclusion of unidirectional molecular motors in hexagonal tris(o‑phenylene) cyclotriphosphazene. J. Am. Chem. Soc. 139, 10486–10498 (2017).
Jiang, X. et al. Crystal fluidity reflected by fast rotational motion at the core, branches, and peripheral aromatic groups of a dendrimeric molecular rotor. J. Am. Chem. Soc. 138, 4650–4656 (2016).
Comotti, A., Bracco, S., Ben, T., Qiu, S. & Sozzani, P. Molecular rotors in porous organic frameworks. Angew. Chem. Int. Ed. 53, 1043–1047 (2014).
Comotti, A. et al. & . Engineering switchable rotors in molecular crystals with open porosity. J. Am. Chem. Soc. 136, 618–621 (2014).
Bracco, S. et al. CO2 regulates molecular rotor dynamics in porous materials. Chem. Commun. 53, 7776–7779 (2017).
Bracco, S. et al. Ultrafast molecular rotors and their CO2 tuning in MOFs with rod-like ligands. Chem. Eur. J. 23, 11210–11215 (2017).
Bracco, S. et al. & . Dipolar rotors orderly aligned in mesoporous fluorinated organosilica architectures. Angew. Chem. Int. Ed. 54, 4773–4777 (2015).
Horike, S. et al. & . Dynamic motion of building blocks in porous coordination polymers. Angew. Chem. Int. Ed. 45, 7226–7230 (2006).
Zhu, K., Vukotic, V. N., Okeefe, C. A., Schurko, R. W. & Loeb, S. J. Metal–organic frameworks with mechanically interlocked pillars: controlling ring dynamics in the solid-state via a reversible phase change. J. Am. Chem. Soc. 136, 7403–7409 (2014).
Elsaidi, S. K. et al. Effect of ring rotation upon gas adsorption in SIFSIX-3-M (M = Fe, Ni) pillared square grid networks. Chem. Sci. 8, 2373–2380 (2017).
Gonzalez-Nelson, A., Coudert, F. X. & van der Veen, M. Rotational dynamics of linkers in metal–organic frameworks. Nanomaterials 9, 330–366 (2019).
Li, H., Eddaoudi, M., O’Keeffe, M. & Yaghi, O. M. Design and synthesis of an exceptionally stable and highly porous metal–organic framework. Nature 402, 276–279 (1999).
Cavka, J. H. et al. & . A new zirconium inorganic building brick forming metal–organic frameworks with exceptional stability. J. Am. Chem. Soc. 130, 13850–13851 (2008).
Yuan, S., Qin, J.-S., Lollar, C. T. & Zhou, H.-C. Stable metal−organic frameworks with group 4 metals: Current status and trends. ACS Cent. Sci. 4, 440–450 (2018).
Owen, N. L. in Internal Rotation in Molecules (ed. Orville‐Thomas, W. J.) Ch. 6 (Wiley, 1974).
Nakagawa, J. & Hayashi, M. Microwave spectrum and internal rotation of 2‐butyne‐1, 1, 1‐d3(dimethylacetylene), CH3C≡CCD3. J. Chem. Phys. 80, 5922–5925 (1984).
Ilyushin, V. et al. Almost free methyl top internal rotation: Rotational spectrum of 2-butynoic acid. J. Mol Spectrosc. 267, 186–190 (2011).
Hensel, K. D. & Gerry, M. C. L. Microwave spectrum of tetrolyl fluoride. J. Chem. Soc. Faraday Trans. 90, 3023–3027 (1994).
Facelli, J. C. et al. & . Low-temperature carbon-13 magnetic resonance in solids. 5. Chemical shielding anisotropy of the 13CH2 group. J. Am. Chem. Soc. 107, 6749–6754 (1985).
Gil, A. M. & Alberti, E. The effect of magic angle spinning on proton spin–lattice relaxation times in some organic solids. Solid State Nucl. Magn. Reson. 11, 203–209 (1998).
Ticko, R. et al. & . Molecular dynamics and the phase transition in solid C60. Phys. Rev. Lett. 67, 1886–1889 (1991).
Panich, A. M. & Panich, E. A. NMR lineshape of a six-spin system with dipole-dipole interactions. Application to benzene. J. Magn. Res. Series A 116, 113–116 (1995).
Goc, R. Computer calculation of the Van Vleck second moment for materials with internal rotation of spin groups. Comput. Phys. Commun. 162, 102–112 (2004).
Kubo, R. & Tomita, K. A general theory of magnetic resonance adsorption. J. Phys. Soc. Jpn 9, 888–919 (1954).
Koksal, F. & Rossler, E. Spin–lattice relaxation by tunneling motions of methyl groups in some organic compounds. Solid State Commun. 44, 233–235 (1982).
Layanowicz, L. Spin–lattice NMR relaxation and second moment of NMR line in solids containing CH3 groups. Concepts Magn. Reson. 44A, 214–225 (2015).
Eibl, K., Kannengießer, R., Stahl, W., Nguyen, H. V. L. & Kleiner, I. Low barrier methyl rotation in 3-pentyn-1-ol as observed by microwave spectroscopy. Molecular Phys. 114, 3483–3489 (2016).
Coelho, A. A. Indexing of powder diffraction patterns by iterative use of singular value decomposition. J. Appl. Cryst. 36, 86–95 (2003).
Coelho, A. A. & Kern, A. Discussion of the indexing algorithms within TOPAS. CPD Newsletter 32, 43–45 (2005).
Macrae, C. F. et al. & . Mercury CSD 2.0 - new features for the vsualization and investigation of crystal structures. J. Appl. Cryst. 41, 466–470 (2008).
Krause, L., Herbst-Irmer, R., Sheldrick, G. M. & Stalke, D. Comparison of silver and molybdenum microfocus X-ray sources for single-crystal structure determination. J. Appl. Cryst 48, 3–10 (2015).
Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. OLEX2: A complete structure solution, refinement and analysis program. J. Appl. Cryst 42, 339–341 (2009).
Sheldrick, G. M. A short history of SHELX. Acta Cryst. A64, 112–122 (2008).
Sheldrick, G. M. Crystal structure refinement with SHELXL. Acta Cryst. C71, 3–8 (2015).
Frisch, M. J. et al. Gaussian 16, Revision B.01 (Gaussian, 2016).
Zhao, Y., Mouhib, H., Li, G., Kleiner, I. & Stahl, W. Conformational analysis of tert-butyl acetate using a combination of microwave spectroscopy and quantum chemical calculations. J. Mol. Spectrosc. 322, 38–42 (2016).
Macho, V., Brombacher, L. & Spiess, H. W. The NMR-WEBLAB: An internet approach to NMR lineshape analysis. Appl. Magn. Reson. 20, 405–432 (2001).
Pecul, M., Dodziuk, H., Jaszunski, M., Lukin, O. & Leszezynski, J. Ab initio calculations of the NMR spectra of [1.1.1]propellane and bicyclo[1.1.1]pentane. Phys. Chem. Chem. Phys. 3, 1986–1991 (1985).
Kubo, R. & Tomita, K. A general theory of magnetic resonance absorption. J. Phys. Soc. Jpn 9, 888–919 (1954).
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.
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 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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