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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References
Novoselov, K. S. et al. Electric field effect in atomically thin carbon films. Science 306, 666–669 (2004).
Li, X. L. et al. Chemically derived, ultrasmooth graphene nanoribbon semiconductors. Science 319, 1229–1232 (2008).
Müllen, K. & Rabe, J. P. Nanographenes as active components of single-molecule electronics and how a scanning tunneling microscope puts them to work. Acc. Chem. Res. 41, 511–520 (2008).
Hernandez, Y. et al. High-yield production of graphene by liquid-phase exfoliation of graphite. Nature Nanotech. 3, 563–568 (2008).
Sutter, P. W., Flege, J. I. & Sutter, E. A. Epitaxial graphene on ruthenium. Nature Mater. 7, 406–411 (2008).
Li, X. et al. Large-area synthesis of high-quality and uniform graphene films on copper foils. Science 324, 1312–1314 (2009).
Berger, C. et al. Electronic confinement and coherence in patterned epitaxial graphene. Science 312, 1191–1196 (2006).
Zhi, L. J. & Müllen, K. A bottom-up approach from molecular nanographenes to unconventional carbon materials. J. Mater. Chem. 18, 1472–1484 (2008).
Rouhanipour, A., Schmaltz, B., Räder, H. J., Pisula, W. & Müllen, K. Filling the cavity of conjugated carbazole macrocycles with graphene molecules: monolayers formed by physisorption serve as a surface for pulsed laser deposition. Angew. Chem. Int. Ed. 48, 720–724 (2009).
Vitali, L. et al. Electronic structure of surface-supported bis(phthalocyaninato) terbium(III) single molecular magnets. Nano Lett. 8, 3364–3368 (2008).
Rauschenbach, S. et al. Electrospray ion-beam deposition of clusters and biomolecules. Small 2, 540–547 (2006).
Satterley, C. J. et al. Electrospray deposition of fullerenes in ultra-high vacuum: in situ scanning tunneling microscopy and photoemission spectroscopy. Nanotechnology 18, 455304 (2007).
Gourdon, A. On-surface covalent coupling in ultrahigh vacuum. Angew. Chem. Int. Ed. 47, 6950–6953 (2008).
Perepichka, D. F. & Rosei, F. Extending polymer conjugation into the second dimension. Science 323, 216–217 (2009).
Lipton-Duffin, J. A. et al. Synthesis of polyphenylene molecular wires by surface-confined polymerization. Small 5, 592–597 (2009).
Treier, M., Richardson, N. V. & Fasel, R. Fabrication of surface-supported low-dimensional polyimide networks. J. Am. Chem. Soc. 130, 14054–14055 (2008).
Treier, M. et al. Molecular imaging of monolayer polyimide formation. Phys. Chem. Chem. Phys. 11, 1209–1214 (2009).
Veld, M. I. et al. Unique intermolecular reaction of simple porphyrins at a metal surface gives covalent nanostructures. Chem. Commun. 1536–1538 (2008).
Grill, L. et al. Nano-architectures by covalent assembly of molecular building blocks. Nature Nanotech. 2, 687–691 (2007).
Matena, M. et al. Transforming surface coordination polymers into covalent surface polymers: linked polycondensed aromatics through oligomerization of N-heterocyclic carbene intermediates. Angew. Chem. Int. Ed. 47, 2414–2417 (2008).
Weigelt, S. et al. Surface synthesis of 2D branched polymer nanostructures. Angew. Chem. Int. Ed. 47, 4406–4410 (2008).
Rim, K. T. et al. Forming aromatic hemispheres on transition-metal surfaces. Angew. Chem. Int. Ed. 46, 7891–7895 (2007).
Otero, G. et al. Fullerenes from aromatic precursors by surface-catalysed cyclodehydrogenation. Nature 454, 865–868 (2008).
Beernink, G. et al. Synthesis of polycyclic aromatic hydrocarbons and graphite islands via surface-induced reaction of small molecules. Chem. Phys. Chem. 2, 317–320 (2001).
Weiss, K. et al. Template-mediated synthesis of polycyclic aromatic hydrocarbons: cyclodehydrogenation and planarization of a hexaphenylbenzene derivative at a copper surface. Angew. Chem. Int. Ed. 38, 3748–3752 (1999).
Fujioka, Y. Studies of polyphenyls and polyphenylenes. 13. Syntheses and physical properties of several polyphenylenes containing mixed linkages. Bull. Chem. Soc. Jpn 57, 3494–3506 (1984).
Rempala, P., Kroulik, J. & King, B. T. Investigation of the mechanism of the intramolecular Scholl reaction of contiguous phenylbenzenes. J. Org. Chem. 71, 5067–5081 (2006).
Rempala, P., Kroulik, J. & King, B. T. A slippery slope: mechanistic analysis of the intramolecular Scholl reaction of hexaphenylbenzene. J. Am. Chem. Soc. 126, 15002–15003 (2004).
Lesnard, H., Bocquet, M. L. & Lorente, N. Dehydrogenation of aromatic molecules under a scanning tunneling microscope: pathways and inelastic spectroscopy simulations. J. Am. Chem. Soc. 129, 4298–4305 (2007).
Lesnard, H., Lorente, N. & Bocquet, M. L. Theoretical study of benzene and pyridine STM-induced reactions on copper surfaces. J. Phys. Condens. Matter 20, 224012 (2008).
Henkelman, G., Uberuaga, B. P. & Jonsson, H. A climbing image nudged elastic band method for finding saddle points and minimum energy paths. J. Chem. Phys. 113, 9901–9904 (2000).
Zwanzig, R. Nonequilibrium Statistical Mechanics (Oxford Univ. Press, 2001).
Rieger, R. et al. Entry to coronene chemistry—making large electron donors and acceptors. Eur. J. Chem. 14, 6322–6325 (2008).
Scholl, R. & Seer, C. Abspaltung aromatisch gebundenen Wasserstoffs und Verknüpfung aromatischer Kerne durch Aluminiumchlorid. Justus Liebigs Ann. Chem. 394, 111–177 (1912).
Bradley, W. & Sutcliffe, F. K. The occurrence of direct hydroxylation and self-condensation in the action of potassium hydroxide on three isomeric benzo-derivatives of meso-benzanthrone. J. Chem. Soc. 1247–1251 (1952).
Pummerer, R., Prell, E. & Rieche, A. Darstellung von Binaphthylendioxyd. Berichte Der Deutschen Chemischen Gesellschaft 59, 2159–2161 (1926).
Hansch, C. & Geiger, C. Notes—a new synthesis for triphenylene. J. Org. Chem. 23, 477–478 (1958).
Kharasch, N. et al. The photochemical conversion of o-terphenyl into triphenylene. Chem. Commun. 242–243 (1965).
Bieri, M. et al. Porous graphenes: two-dimensional polymer synthesis with atomic precision. Chem. Commun. 6919–6921 (2009).
Gutzler, R. et al. Surface mediated synthesis of 2D covalent organic frameworks: 1,3,5-tris(4-bromophenyl)benzene on graphite(001), Cu(111) and Ag(110). Chem. Commun. 4456–4458 (2009).
Xue, X. & Scott, L. T. Thermal cyclodehydrogenations to form 6-membered rings: cyclizations of [5]helicenes. Org. Lett. 9, 3937–3940 (2007).
Pignedoli, C. A. et al. A simple approach for describing metal-supported cyclohexaphenylene dehydrogenation. Eur. Phys. J. B 75, 65–70 (2010).
Ruffieux, P. et al. Self-assembly of extended polycyclic aromatic hydrocarbons on Cu(111). J. Phys. Chem. B 110, 11253–11258 (2006).
Horcas, I. et al. WSXM: a software for scanning probe microscopy and a tool for nanotechnology. Rev. Sci. Instrum. 78, 013705 (2007).
VandeVondele, J. et al. QUICKSTEP: fast and accurate density functional calculations using a mixed Gaussian and plane waves approach. Comput. Phys. Commun. 167, 103–128 (2005).
Grimme, S. Semiempirical GGA-type density functional constructed with a long-range dispersion correction. J. Comput. Chem. 27, 1787–1799 (2006).
Perdew, J. P., Burke, K. & Wang, Y. Generalized gradient approximation for the exchange-correlation hole of a many-electron system. Phys. Rev. B 54, 16533–16539 (1996).
Goedecker, S., Teter, M. & Hutter, J. Separable dual-space Gaussian pseudopotentials. Phys. Rev. B 54, 1703–1710 (1996).
Laio, A. & Parrinello, M. Escaping free-energy minima. Proc. Natl Acad. Sci. USA 99, 12562–12566 (2002).
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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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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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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DOI: https://doi.org/10.1038/nchem.891
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