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Unidirectional rotary motion in a metal–organic framework

Abstract

Overcrowded alkene-based light-driven molecular motors are able to perform large-amplitude repetitive unidirectional rotations. Their behaviour is well understood in solution. However, Brownian motion precludes the precise positioning at the nanoscale needed to harness cooperative action. Here, we demonstrate molecular motors organized in crystalline metal–organic frameworks (MOFs). The motor unit becomes a part of the organic linker (or strut), and its spatial arrangement is elucidated through powder and single-crystal X-ray analyses and polarized optical and Raman microscopies. We confirm that the light-driven unidirectional rotation of the motor units is retained in the MOF framework and that the motors can operate in the solid state with similar rotary speed (rate of thermal helix inversion) to that in solution. These ‘moto-MOFs’ could in the future be used to control dynamic function in crystalline materials.

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Fig. 1: Design of the moto-MOF.
Fig. 2: Schematic representation of the synthesis of the moto-MOFs.
Fig. 3: Structure of moto-MOF1 material.
Fig. 4: Photochemical and thermal isomerization of 1 in solution.
Fig. 5: Photochemical and thermal isomerization studies of 1 in moto-MOF1.

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Data availability

The data associated with the reported findings are available in the manuscript or the Supplementary Information. Other related data are available from the corresponding author upon request.

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Acknowledgements

This work was supported financially by the Netherlands Organisation for Scientific Research (NWO), the European Research Council (ERC, advanced grant no. 694345 to B.L.F.), the Ministry of Education, Culture and Science (Gravitation Program no. 024.001.035). The authors thank P. van der Meulen for assistance with NMR irradiation experiments, J. Baas for help with acquiring PXRD, M. Lutz and E. Otten for measurement and analysis of single crystal X-ray data and F. (K.-C.) Leung for making the 3D model of the moto-MOF. The authors thank the University of Groningen for access to the Peregrine Computing Cluster.

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W.D., S.J.W. and B.L.F. conceived the project. W.D. and D.R. synthesized compounds and W.D. carried out studies in solution. W.D., S.A. and W.R.B. performed Raman micro-spectroscopy studies of the solid material. W.D and T.v.L. performed DFT studies. S.J.W., W.R.B. and B.L.F. guided the project. W.D., T.v.L., S.J.W. and B.L.F. wrote the manuscript. All authors discussed the results and commented on the manuscript.

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Correspondence to Wesley R. Browne, Sander J. Wezenberg or Ben L. Feringa.

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Supplementary Figures 1–84; Supplementary Schemes 1,2

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Danowski, W., van Leeuwen, T., Abdolahzadeh, S. et al. Unidirectional rotary motion in a metal–organic framework. Nat. Nanotechnol. 14, 488–494 (2019). https://doi.org/10.1038/s41565-019-0401-6

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