A chemically powered unidirectional rotary molecular motor based on a palladium redox cycle


The conversion of chemical energy to drive directional motion at the molecular level allows biological systems, ranging from subcellular components to whole organisms, to perform a myriad of dynamic functions and respond to changes in the environment. Directional movement has been demonstrated in artificial molecular systems, but the fundamental motif of unidirectional rotary motion along a single-bond rotary axle induced by metal-catalysed transformation of chemical fuels has not been realized, and the challenge is to couple the metal-centred redox processes to stepwise changes in conformation to arrive at a full unidirectional rotary cycle. Here, we present the design of an organopalladium-based motor and the experimental demonstration of a 360° unidirectional rotary cycle using simple chemical fuels. Exploiting fundamental reactivity principles in organometallic chemistry enables control of directional rotation and offers the potential of harnessing the wealth of opportunities offered by transition-metal-based catalytic conversions to drive motion and dynamic functions.

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Figure 1: Concept and design of a unidirectional rotary molecular motor.
Figure 2: Palladium-mediated 360° unidirectional rotation of biaryl 1.
Figure 3: Unidirectional 180° rotation of (S,M)-1 into (S,P)-1.
Figure 4: Unidirectional 180° rotation of (S,P)-1 into (S,M)-1.
Figure 5: Chemical structures and reaction scheme for an integrated cycle based on switching palladium(II) and palladium(0) redox states for unidirectional 360° rotation of (S,M)-1 into (S,P)-1 into (S,M)-1.


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This work was supported financially by the European Research Council (Advanced Investigator Grant no. 227897 to B.L.F.), The Netherlands Organization for Scientific Research (NWO-CW), funding from the Ministry of Education and Science (Gravitation programme 024.001.035) and The Royal Netherlands Academy of Arts and Sciences (KNAW).

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B.S.L.C. and B.L.F. conceived the project. B.S.L.C. performed the experimental work. J.C.M.K. performed the computational chemistry. E.O. solved the crystal structures. B.S.L.C. and B.L.F. wrote the manuscript. All authors read and commented on the manuscript.

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Correspondence to Ben L. Feringa.

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The authors declare no competing financial interests.

Supplementary information

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Supplementary information (PDF 5787 kb)

Supplementary information

Crystallographic data for compound (+-)-Pd[(R,M)-3]BrPCy3 (CIF 1871 kb)

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Crystallographic data for compound (S,M)-1 (CIF 843 kb)

Supplementary information

Crystallographic data for compound (S,P)-1 (CIF 1602 kb)

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Collins, B., Kistemaker, J., Otten, E. et al. A chemically powered unidirectional rotary molecular motor based on a palladium redox cycle. Nature Chem 8, 860–866 (2016). https://doi.org/10.1038/nchem.2543

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