Nano-architectures by covalent assembly of molecular building blocks


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 options

Rent or Buy article

Get time limited or full article access on ReadCube.


All prices are NET prices.

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.


  1. 1

    Joachim, C., Gimzewski, J. K. & Aviram, A. Electronics using hybrid-molecular and mono-molecular devices. Nature 408, 541–548 (2000).

    CAS  Article  Google Scholar 

  2. 2

    Heath, J. R. & Ratner, M. A. Molecular electronics. Physics Today 56, 43–49 (2003).

    CAS  Article  Google Scholar 

  3. 3

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

    CAS  Article  Google Scholar 

  4. 4

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

    CAS  Article  Google Scholar 

  5. 5

    Whitesides, G. M. & Grzybowski, B. Self-assembly at all scales. Science 295, 2418–2421 (2002).

    CAS  Article  Google Scholar 

  6. 6

    Theobald, J. A., Oxtoby, N. S., Phillips, M. A., Champness, N. R. & Beton, P. H. Controlling molecular deposition and layer structure with supramolecular surface assemblies. Nature 424, 1029–1031 (2003).

    CAS  Article  Google Scholar 

  7. 7

    Barth, J. V., Costantini, G. & Kern, K. Engineering atomic and molecular nanostructures at surfaces. Nature 437, 671–679 (2005).

    CAS  Article  Google Scholar 

  8. 8

    Barth, J. V., Weckesser, J., Lin, N., Dmitriev, A. & Kern, K. Supramolecular architectures and nanostructures at metal surfaces. Appl. Phys. A 76, 645–652 (2003).

    CAS  Article  Google Scholar 

  9. 9

    Pawin, G., Wong, K. L., Kwon, K.-Y. & Bartels, L. A homomolecular porous network at a Cu(111) surface. Science 313, 961–962 (2006).

    CAS  Article  Google Scholar 

  10. 10

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

    CAS  Article  Google Scholar 

  11. 11

    Stöhr, M. 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).

    Article  Google Scholar 

  12. 12

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

    CAS  Article  Google Scholar 

  13. 13

    Yokoyama, T., Yokoyama, S., Kamikado, T., Okuno, Y. & Mashiko, S. Selective assembly on a surface of supramolecular aggregates with controlled size and shape. Nature 413, 619–621 (2001).

    CAS  Article  Google Scholar 

  14. 14

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

    CAS  Article  Google Scholar 

  15. 15

    Lin, N., Dmitriev, A., Weckesser, J., Barth, J. V. & Kern, K. Real-time single-molecule imaging of the formation and dynamics of coordination compounds. Angew. Chem. Int. Edn 41, 4779–4783 (2002).

    CAS  Article  Google Scholar 

  16. 16

    Hla, S. W., Bartels, L., Meyer, G. & Rieder, K.-H. Inducing all steps of a chemical reaction with the scanning tunneling microscope tip: towards single molecule engineering. Phys. Rev. Lett. 85, 2777–2780 (2000).

    CAS  Article  Google Scholar 

  17. 17

    Hla, S.-W., Meyer, G. & Rieder, K.-H. Selective bond breaking of single iodobenzene molecules with a scanning tunneling microscope tip. Chem. Phys. Lett. 370, 431–436 (2003).

    CAS  Article  Google Scholar 

  18. 18

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

    CAS  Article  Google Scholar 

  19. 19

    Iancu, V., Deshpande, A. & Hla, S.-W. Manipulation of the Kondo effect via two-dimensional molecular assembly. Phys. Rev. Lett. 97, 266603 (2006).

    Article  Google Scholar 

  20. 20

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

    CAS  Article  Google Scholar 

  21. 21

    Zambelli, T. 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).

    CAS  Article  Google Scholar 

  22. 22

    Gottfried, J. M., Flechtner, K., Kretschmann, A., Lukasczyk, T. & Steinrück, H.-P. Direct synthesis of a metalloporphyrin complex on a surface. J. Am. Chem. Soc. 128, 5644–5645 (2006).

    CAS  Article  Google Scholar 

Download references


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




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

Supplementary Information

Supplementary information including synthesis, methods and figures (PDF 779 kb)

Rights and permissions

Reprints and Permissions

About this article

Cite this article

Grill, L., Dyer, M., Lafferentz, L. et al. Nano-architectures by covalent assembly of molecular building blocks. Nature Nanotech 2, 687–691 (2007).

Download citation

Further reading


Find nanotechnology articles, nanomaterial data and patents all in one place. Visit Nano by Nature Research