Abstract
One of the major challenges for harnessing the true potential of functional nano-machinery is integrating and transmitting motion with great precision. Molecular gearing systems enable the integration of multiple motions in a correlated fashion to translate motions from one locality to another and to change their speed and direction. However, currently no powerful methods exist to implement active driving of gearing motions at the molecular scale. Here we present a light-fuelled molecular gearing system and demonstrate its superiority over passive thermally activated gearing. Translation of a 180° rotation into a 120° rotation is achieved while at the same time the direction of the rotation axis is shifted by 120°. Within such photogearing processes, precise motions at the nanoscale can be changed in direction and decelerated in a manner similar to macroscopic bevel-gear operations in an energy consuming way—a necessary prerequisite to employ gearing as an active component in future mechanical nano-systems.
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Data availability
All data supporting the findings of this study are available in the Article and the associated Supplementary Information files; the same data can also be obtained from the corresponding author on reasonable request. The X-ray crystallographic coordinates for the structures 1 (A) and 1 (C) reported in this study have been deposited at the Cambridge Crystallographic Data Centre (CCDC), under CCDC numbers 2086150 (1 (A)) and 2086149 (1 (C)). These data can be obtained free of charge from the Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif. Source data are provided with this paper.
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Acknowledgements
H.D. acknowledges support from the Deutsche Forschungsgemeinschaft (DFG, Emmy Noether fellowship DU 1414/1-2 and SFB 749, A12). H.D. thanks the Cluster of Excellence ‘Center for Integrated Protein Science Munich’ (CIPSM) for financial support.
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A.G. and H.D. designed the molecular setup and experiments. A.G. and F.G. synthesized and characterized HTI-photogear 1 and conducted the photophysical, photochemical and kinetic experiments as well as quantitative analyses. P.M. determined the molecular structures in the crystalline state. H.D. coordinated the study and wrote the manuscript. All authors read and approved the paper.
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Nature Chemistry thanks Wataru Setaka and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.
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Supplementary information
Supplementary Information
Experimental details, Supplementary –Sections 1–4.8, Figs. 1–87, Tables 1–9 and equations 1–44.
Supplementary Video 1
Animated photogearing from isomer C to isomer B′.
Supplementary Video 2
Animated photogearing from isomer C to isomer B.
Supplementary Video 3
Animated photogearing from isomer D to isomer A.
Supplementary Video 4
Animated photogearing from isomer D to isomer B′.
Supplementary Data 1
XY data for all plots and numerical values for diagrams included in the supplementary information.
Supplementary Data 2
Crystallographic data for isomers C and A, with CCDC reference numbers 2086149 and 2086150, respectively.
Source data
Source Data Fig. 2
XY data for panels c and d; numerical values for panel e.
Source Data Fig. 3
XY data for panels b–g.
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Gerwien, A., Gnannt, F., Mayer, P. et al. Photogearing as a concept for translation of precise motions at the nanoscale. Nat. Chem. 14, 670–676 (2022). https://doi.org/10.1038/s41557-022-00917-0
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DOI: https://doi.org/10.1038/s41557-022-00917-0