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Surface-assisted cyclodehydrogenation provides a synthetic route towards easily processable and chemically tailored nanographenes

Nature Chemistry volume 3, pages 61–67 (2011)Cite this article

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Abstract

Atomically thin sheets of sp2-hybridized carbon—graphene—have enormous potential for applications in future electronic devices. Particularly promising are nanostructured (sub)units of graphene, the electronic properties of which can be tuned by changing the spatial extent or the specific edge termination of the carbon network. Processability and precise tailoring of graphene-derived structures are, however, still major obstacles in developing applications; both bottom-up and top-down routes are presently under investigation in attempts to overcome this limitation. Here, we propose a surface chemical route that allows for the atomically precise fabrication of tailored nanographenes from polyphenylene precursors. The cyclodehydrogenation of a prototypical polyphenylene on Cu(111) is studied using scanning tunnelling microscopy and density functional theory. We find that the thermally induced cyclodehydrogenation proceeds via several intermediate steps, two of which can be stabilized on the surface, yielding unprecedented insight into a dehydrogenative intramolecular aryl–aryl coupling reaction.

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Figure 1
Figure 2: Overview STM images of CHP cyclodehydrogenation on Cu(111).
Figure 3: High-resolution STM images of reactant, intermediates and final product on Cu(111).
Figure 4: Relaxed geometry of CHP on Cu(111).
Figure 5: Computational simulations of surface-supported cyclodehydrogenation.

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Acknowledgements

The authors acknowledge financial support from the Swiss National Science Foundation and the generous allocation of computing time at the CSCS. The authors thank P. Ruffieux for stimulating discussions and T. Greber for providing access to his NearNode-endstation for the XPD experiments. Parts of these experiments were performed on the SIM beamline at the Swiss Light Source, Paul Scherrer Institut, Villigen, Switzerland.

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Author notes

  1. Matthias Treier & Teodoro Laino

    Present address: Present address: Institut de Science et d'Ingénierie Supramoléculaires, Université de Strasbourg, 67000 Strasbourg, France (M.T.); IBM Zurich Research Laboratory, 8803 Rueschlikon, Switzerland (T.L),

Authors and Affiliations

  1. Empa, Swiss Federal Laboratories for Materials Science and Technology, nanotech@surfaces laboratory, 3602 Thun and 8600 Dübendorf, Switzerland

    Matthias Treier, Carlo Antonio Pignedoli, Daniele Passerone & Roman Fasel

  2. Physical Chemistry Institute, University of Zurich, Winterthurerstrasse 190, Zurich, 8057, Switzerland

    Teodoro Laino

  3. Max-Planck Institute for Polymer Research, Mainz, 55128, Germany

    Ralph Rieger & Klaus Müllen

  4. Department of Chemistry and Biochemistry, University of Bern, Bern, 3012, Switzerland

    Roman Fasel

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Contributions

M.T. performed the STM measurements, analysed the data and wrote the manuscript together with C.P. and R.F. C.P. and T.L. performed the simulations in collaboration with D.P. R.R. synthesized the molecular substances under the supervision of K.M. R.F. conceived the experiments and coordinated the work. All authors discussed the results and commented on the manuscript.

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Correspondence to Roman Fasel.

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Treier, M., Pignedoli, C., Laino, T. et al. Surface-assisted cyclodehydrogenation provides a synthetic route towards easily processable and chemically tailored nanographenes. Nature Chem 3, 61–67 (2011). https://doi.org/10.1038/nchem.891

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