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Nano-architectures by covalent assembly of molecular building blocks

Nature Nanotechnology volume 2, pages 687–691 (2007)Cite this article

Abstract

The construction of electronic devices from single molecular building blocks, which possess certain functions such as switching or rectifying and are connected by atomic-scale wires on a supporting surface, is an essential goal of molecular electronics1. A key challenge is the controlled assembly of molecules into desired architectures by strong, that is, covalent, intermolecular connections2, enabling efficient electron transport3 between the molecules and providing high stability4. However, no molecular networks on surfaces ‘locked’ by covalent interactions have been reported so far. Here, we show that such covalently bound molecular nanostructures can be formed on a gold surface upon thermal activation of porphyrin building blocks and their subsequent chemical reaction at predefined connection points. We demonstrate that the topology of these nanostructures can be precisely engineered by controlling the chemical structure of the building blocks. Our results represent a versatile route for future bottom-up construction of sophisticated electronic circuits and devices, based on individual functionalized molecules.

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Figure 1: Nano-architectures of covalently bound Br4TPP molecular networks.
Figure 2: Controlling the macromolecular architecture.
Figure 3: Signature of the covalent character of the intermolecular bonds.
Figure 4: Weak and strong intermolecular forces in lateral manipulation.

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Acknowledgements

We thank F. Moresco for discussions. This work was supported by the Deutsche Forschungsgemeinschaft (DFG) through contract no. GR 2697/1-1 and by the European Union through the Integrated Project PICO INSIDE and the Marie-Curie Research Training Network PRAIRIES, contract MRTN-CT-2006-035810. M.P. is grateful for support from the Humboldt foundation and the Swedish Research Council (VR).

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Authors and Affiliations

  1. Institut für Experimentalphysik, Freie Universität Berlin, Arnimallee 14, Berlin, 14195, Germany

    Leonhard Grill & Leif Lafferentz

  2. Surface Science Research Centre and Department of Chemistry, University of Liverpool, Liverpool, L69 3BX, UK

    Matthew Dyer & Mats Persson

  3. Institut für Chemie, Humboldt-Universität zu Berlin, Brook-Taylor-Str. 2, Berlin, 12489, Germany

    Maike V. Peters & Stefan Hecht

Authors
  1. Leonhard Grill
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  4. Mats Persson
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Contributions

L.G. and S.H. conceived the experiments. L.G. performed the experiments (partly with L.L.) and analysed the data. M.D. and M.P. were in charge of the calculations. M.V.P. and S.H. synthesized the molecules. L.G. wrote the paper. L.G., M.D., M.P. and S.H. discussed the results and commented on the manuscript.

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Correspondence to Leonhard Grill or Stefan Hecht.

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Grill, L., Dyer, M., Lafferentz, L. et al. Nano-architectures by covalent assembly of molecular building blocks. Nature Nanotech 2, 687–691 (2007). https://doi.org/10.1038/nnano.2007.346

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