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Formylation boosts the performance of light-driven overcrowded alkene-derived rotary molecular motors

Nature Chemistry (2024)Cite this article

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Abstract

Artificial molecular motors and machines constitute a critical element in the transition from individual molecular motion to the creation of collective dynamic molecular systems and responsive materials. The design of artificial light-driven molecular motors operating with high efficiency and selectivity constitutes an ongoing fundamental challenge. Here we present a highly versatile synthetic approach based on Rieche formylation that boosts the quantum yield of the forward photoisomerization reaction while reaching near-perfect selectivity in the steps involved in the unidirectional rotary cycle and drastically reducing competing photoreactions. This motor is readily accessible in its enantiopure form and operates with nearly quantitative photoconversions. It can easily be functionalized further and outperforms its direct predecessor as a reconfigurable chiral dopant in cholesteric liquid crystal materials.

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Fig. 1: Conceptual illustration of rotary motion of typical molecular motors and boosted molecular motor system.
Fig. 2: Unidirectional rotary cycle of motor 1.
Fig. 3: Comparison of motors 1 and 2 and transient absorption spectroscopy studies of 1.
Fig. 4: Synthesis and characterization of second-generation motors.
Fig. 5: Multistate characterizations and application in LC doping.

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Data availability

The online version of this paper provides Supplementary Information, encompassing supplementary figures, general methods, detailed experimental and analytical data, NMR spectra and SFC chromatograms, as well as all other supporting data for the study. Source data are provided with this paper. All the unprocessed data are available from the corresponding author upon reasonable request. Crystallographic data for the structures reported in this Article have been deposited at the Cambridge Crystallographic Data Centre (CCDC) under deposition numbers CCDC 2170238 (4st), CCDC 2170239 (Z-1st), CCDC 2170240 (E-1st), CCDC 2264532 (Z-S1st) and CCDC 2264533 (E-S1st). Copies of the data can be obtained free of charge via https://www.ccdc.cam.ac.uk/structures/.

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Acknowledgements

This work was supported by the China Scholarship Council (CSC PhD fellowship no. 201808330459 to J.S.) and financial support from The Netherlands Organization for Scientific Research (NWO-CW), the Dutch Ministry of Education, Culture and Science (Gravitation programme no. 024.001.035). We acknowledge R. Sneep for mass spectral analysis and SFC training. We thank R. Toyoda for the X-ray structure analysis; Q. Zhang for fruitful discussions; and S. Wezenberg, J. de Jong and A. Faulker for work on structurally related motors. W.D. greatly acknowledges G. Ragazzon for the discussion on the kinetic asymmetry of light-driven motors. Correspondence and requests for materials should be sent to Ben Feringa b.l.feringa@rug.nl.

Author information

Author notes

  1. Stefano Crespi

    Present address: Department of Chemistry, Ångström Laboratory, Uppsala University, Uppsala, Sweden

Authors and Affiliations

  1. Stratingh Institute for Chemistry, University of Groningen, Groningen, The Netherlands

    Jinyu Sheng, Wojciech Danowski, Andy S. Sardjan, Jiaxin Hou, Stefano Crespi, Alexander Ryabchun, Wesley R. Browne & Ben L. Feringa

  2. Institute of Supramolecular Science and Engineering (ISIS), Université de Strasbourg, CNRS, Strasbourg, France

    Wojciech Danowski

  3. Faculty of Chemistry, University of Warsaw, Warsaw, Poland

    Wojciech Danowski

  4. Van ’t Hoff Institute for Molecular Sciences, University of Amsterdam, Amsterdam, The Netherlands

    Maximilian Paradiz Domínguez & Wybren Jan Buma

  5. Institute for Molecules and Materials, FELIX Laboratory, Radboud University, Nijmegen, The Netherlands

    Wybren Jan Buma

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Contributions

J.S., W.D. and B.L.F. conceived the project. B.L.F. and W.D. guided and supervised the research. J.S. and W.D. synthesized the compounds. J.S. led the project and carried out all experimental studies and characterizations. S.C. conducted computations. A.S.S. and M.P.D. performed the transient absorption spectroscopy measurements and 1H NMR QY measurements. J.H., A.R. and J.S. performed the LC doping measurements. J.S., W.D., W.J.B. and B.L.F. wrote the manuscript. All authors discussed the results and commented on the manuscript.

Corresponding author

Correspondence to Ben L. Feringa.

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Nature Chemistry thanks Stefano Corra and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information

Supplementary Figs. 1–65, Tables 1–10 and Discussion.

Supplementary Data 1

Raw NMR data for Figs. 2c, 4d,g and 5a.

Supplementary Data 2

Crystallographic data for compound 4st; CCDC reference 2170238.

Supplementary Data 3

Crystallographic data for compound Z-1st; CCDC reference 2170239.

Supplementary Data 4

Crystallographic data for compound E-1st; CCDC reference 2170240.

Supplementary Data 5

Crystallographic data for compound Z-S1st; CCDC reference 2264532.

Supplementary Data 6

Crystallographic data for compound E-S1st; CCDC reference 2264533.

Source data

Source Data Fig. 2

Compilation of UV–visible spectra. Source Data Fig. 3 Compilation of UV–visible spectra, time-course photoconversion and histogram of QY along uncertainties of the fit. Source Data Fig. 4 Compilation of UV–visible spectra. Source Data Fig. 5 Compilation of CD spectra.

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Sheng, J., Danowski, W., Sardjan, A.S. et al. Formylation boosts the performance of light-driven overcrowded alkene-derived rotary molecular motors. Nat. Chem. (2024). https://doi.org/10.1038/s41557-024-01521-0

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