Letter | Published:

Nano-architectures by covalent assembly of molecular building blocks

Nature Nanotechnology volume 2, pages 687691 (2007) | Download Citation

Subjects

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.

Access optionsAccess options

Rent or Buy article

Get time limited or full article access on ReadCube.

from$8.99

All prices are NET prices.

References

  1. 1.

    , & Electronics using hybrid-molecular and mono-molecular devices. Nature 408, 541–548 (2000).

  2. 2.

    & Molecular electronics. Physics Today 56, 43–49 (2003).

  3. 3.

    & Electron transport in molecular wire junctions. Science 300, 1384–1389 (2003).

  4. 4.

    et al. Porous, crystalline, covalent organic frameworks. Science 310, 1166–1170 (2005).

  5. 5.

    & Self-assembly at all scales. Science 295, 2418–2421 (2002).

  6. 6.

    , , , & Controlling molecular deposition and layer structure with supramolecular surface assemblies. Nature 424, 1029–1031 (2003).

  7. 7.

    , & Engineering atomic and molecular nanostructures at surfaces. Nature 437, 671–679 (2005).

  8. 8.

    , , , & Supramolecular architectures and nanostructures at metal surfaces. Appl. Phys. A 76, 645–652 (2003).

  9. 9.

    , , & A homomolecular porous network at a Cu(111) surface. Science 313, 961–962 (2006).

  10. 10.

    et al. Macroscopic hierarchical surface patterning of porphyrin trimers via self-assembly and dewetting. Science 314, 1433–1436 (2006).

  11. 11.

    et al. Controlling molecular assembly in two dimensions: The concentration dependence of thermally induced 2D aggregation of molecules on a metal surface. Angew. Chem. Int. Edn 44, 7394–7398 (2005).

  12. 12.

    et al. Assembly and processing of hydrogen bond induced supramolecular nanostructures. Nano Lett. 3, 9–12 (2003).

  13. 13.

    , , , & Selective assembly on a surface of supramolecular aggregates with controlled size and shape. Nature 413, 619–621 (2001).

  14. 14.

    & Commensurability and mobility in two-dimensional molecular patterns on graphite. Science 253, 424–427 (1991).

  15. 15.

    , , , & Real-time single-molecule imaging of the formation and dynamics of coordination compounds. Angew. Chem. Int. Edn 41, 4779–4783 (2002).

  16. 16.

    , , & Inducing all steps of a chemical reaction with the scanning tunneling microscope tip: towards single molecule engineering. Phys. Rev. Lett. 85, 2777–2780 (2000).

  17. 17.

    , & Selective bond breaking of single iodobenzene molecules with a scanning tunneling microscope tip. Chem. Phys. Lett. 370, 431–436 (2003).

  18. 18.

    et al. A two-dimensional porphyrin-based porous network featuring communicating cavities for the templated complexation of fullerenes. Adv. Mater. 18, 275–279 (2006).

  19. 19.

    , & Manipulation of the Kondo effect via two-dimensional molecular assembly. Phys. Rev. Lett. 97, 266603 (2006).

  20. 20.

    & Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B 54, 11169–11186 (1996).

  21. 21.

    et al. Deposition of large organic molecules in ultra-high vacuum: A comparison between thermal sublimation and pulse-injection. Int. J. Nanosci. 3, 331–341 (2004).

  22. 22.

    , , , & Direct synthesis of a metalloporphyrin complex on a surface. J. Am. Chem. Soc. 128, 5644–5645 (2006).

Download references

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).

Author information

Affiliations

  1. Institut für Experimentalphysik, Freie Universität Berlin, Arnimallee 14, 14195 Berlin, 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, 12489 Berlin, Germany

    • Maike V. Peters
    •  & Stefan Hecht

Authors

  1. Search for Leonhard Grill in:

  2. Search for Matthew Dyer in:

  3. Search for Leif Lafferentz in:

  4. Search for Mats Persson in:

  5. Search for Maike V. Peters in:

  6. Search for Stefan Hecht in:

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.

Corresponding authors

Correspondence to Leonhard Grill or Stefan Hecht.

Supplementary information

PDF files

  1. 1.

    Supplementary Information

    Supplementary information including synthesis, methods and figures

About this article

Publication history

Received

Accepted

Published

DOI

https://doi.org/10.1038/nnano.2007.346

Further reading