Electrically driven directional motion of a four-wheeled molecule on a metal surface

Abstract

Propelling single molecules in a controlled manner along an unmodified surface remains extremely challenging because it requires molecules that can use light, chemical or electrical energy to modulate their interaction with the surface in a way that generates motion. Nature’s motor proteins1,2 have mastered the art of converting conformational changes into directed motion, and have inspired the design of artificial systems3 such as DNA walkers4,5 and light- and redox-driven molecular motors6,7,8,9,10,11. But although controlled movement of single molecules along a surface has been reported12,13,14,15,16, the molecules in these examples act as passive elements that either diffuse along a preferential direction with equal probability for forward and backward movement or are dragged by an STM tip. Here we present a molecule with four functional units—our previously reported rotary motors6,8,17—that undergo continuous and defined conformational changes upon sequential electronic and vibrational excitation. Scanning tunnelling microscopy confirms that activation of the conformational changes of the rotors through inelastic electron tunnelling propels the molecule unidirectionally across a Cu(111) surface. The system can be adapted to follow either linear or random surface trajectories or to remain stationary, by tuning the chirality of the individual motor units. Our design provides a starting point for the exploration of more sophisticated molecular mechanical systems with directionally controlled motion.

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Figure 1: Structure of the four-wheeled molecule.
Figure 2: Linear movement of the meso-(R,S-R,S ) isomer.
Figure 3: Helix inversion at lower bias voltage and polarity dependence of propulsion.
Figure 4: Control over motion by the geometries of the four motors.

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Acknowledgements

This research was supported by the Netherlands Organization for Scientific Research (NWO-CW) (B.L.F. and T.K. through a VENI grant), the Swiss Secretary for Education and Research and the Swiss National Science Foundation (K.-H.E. and M.P.), and the European Research Council (ERC advanced grant 227897 to B.L.F.).

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Authors

Contributions

N.R., B.M., S.R.H. and B.L.F. designed the four-wheeled molecule and N.R. conducted its synthesis and characterization. T.K., M.P., N.K. and K.-H.E. designed the STM experiments and contributed to their interpretation. T.K. and M.P. performed the STM experiments at Empa. T.K., K.-H.E. and B.L.F. wrote the manuscript. S.R.H., K.-H.E. and B.L.F. conceived and guided the research. All authors discussed the results and implications and commented on the manuscript at all stages.

Corresponding authors

Correspondence to Syuzanna R. Harutyunyan or Karl-Heinz Ernst or Ben L. Feringa.

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The authors declare no competing financial interests.

Supplementary information

Supplementary Information

This file contains Supplementary Information comprising Supplementary Sections 1-5 (see Contents), which include a Supplementary Discussion, Supplementary Text and Data, Supplementary Figures 1-10 with legends and full legends for Supplementary Movies 1-4. (PDF 2725 kb)

Supplementary Movie 1

In this movie we see preferentially linear movement of the meso-isomer of the four-wheeled molecule after excitation - see Supplementary Information for full legend. (MOV 185 kb)

Supplementary Movie 2

In this movie we see changes in STM contrast induced by helix inversion of the motor units of the four-wheeled molecule after vibrational excitation - see Supplementary Information for full legend. (MOV 162 kb)

Supplementary Movie 3

In this movie we see the random movement of one enantiomer of the racemic version of the four-wheeled molecule after excitation - see Supplementary Information for full legend. (MOV 850 kb)

Supplementary Movie 4

In this movie we see a molecular model for the anticipated linear propulsion of the meso-form of the four-wheeled molecule - see Supplementary Information for full legend. (MOV 800 kb)

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Kudernac, T., Ruangsupapichat, N., Parschau, M. et al. Electrically driven directional motion of a four-wheeled molecule on a metal surface. Nature 479, 208–211 (2011). https://doi.org/10.1038/nature10587

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