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Simultaneous and coordinated rotational switching of all molecular rotors in a network

Nature Nanotechnology volume 11, pages 706–712 (2016)Cite this article

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Abstract

A range of artificial molecular systems has been created that can exhibit controlled linear and rotational motion. In the further development of such systems, a key step is the addition of communication between molecules in a network. Here, we show that a two-dimensional array of dipolar molecular rotors can undergo simultaneous rotational switching when applying an electric field from the tip of a scanning tunnelling microscope. Several hundred rotors made from porphyrin-based double-decker complexes can be simultaneously rotated when in a hexagonal rotor network on a Cu(111) surface by applying biases above 1 V at 80 K. The phenomenon is observed only in a hexagonal rotor network due to the degeneracy of the ground-state dipole rotational energy barrier of the system. Defects are essential to increase electric torque on the rotor network and to stabilize the switched rotor domains. At low biases and low initial rotator angles, slight reorientations of individual rotors can occur, resulting in the rotator arms pointing in different directions. Analysis reveals that the rotator arm directions are not random, but are coordinated to minimize energy via crosstalk among the rotors through dipolar interactions.

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Figure 1: Structure and self-assembly of molecular rotors.
Figure 2: Simultaneous rotations.
Figure 3: Rotation mechanisms.
Figure 4: Electric torque and coordinated reorientations.

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Acknowledgements

This work (all the STM experiments as well as analytical and DFT calculations) is financially supported by the United State Department of Energy, Basic Energy Sciences grant no. DE-FG02-02ER46012. R.S., J.E., C.J. and G.R. acknowledge support from ANR P3N (AUTOMOL project no. ANR 09-NANO-040) for the chemical synthesis of molecules and STM image calculations. The authors acknowledge ZYVEX for providing the molecules studied in the initial part of the project. S.W.H. and K.F.B. acknowledge the use of the Ohio Supercomputing Centre (PHS0275).

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Authors and Affiliations

  1. Physics and Astronomy Department, Nanoscale and Quantum Phenomena Institute, Ohio University, Athens, 45701, Ohio, USA

    Y. Zhang, H. Kersell, V. Iancu, U. G. E. Perera, Y. Li, A. Deshpande, K.-F. Braun & S.-W. Hla

  2. CEMES, CNRS, 29 rue J. Marvig, Toulouse, 31055, France

    R. Stefak, J. Echeverria, C. Joachim & G. Rapenne

  3. Universite’ de Toulouse, UPS, 118 route de Narbonne, Toulouse, 31062, France

    G. Rapenne

  4. Nanoscience and Technology Division, Center for Nanoscale Materials, Argonne National Laboratory, 60439, Illinois, USA

    S.-W. Hla

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Contributions

S.W.H. conceived and designed the experiments. Y.Z., H.K., V.I., G.P., Y.L. and A.D. performed the STM experiments. R.S. and G.R. synthesized the molecules. J.E. and C.J. performed STM image, adsorption site and rotational barrier calculations. K.F.B., Y.Z. and S.W.H. performed the DFT and analytical calculations. Y.Z., H.K., V.I. and S.W.H. analysed the experimental data. All authors discussed the results and commented on the manuscript.

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Correspondence to S.-W. Hla.

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Zhang, Y., Kersell, H., Stefak, R. et al. Simultaneous and coordinated rotational switching of all molecular rotors in a network. Nature Nanotech 11, 706–712 (2016). https://doi.org/10.1038/nnano.2016.69

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