Metal–organic coordination networks (MOCNs) have attracted wide interest because they provide a novel route towards porous materials that may find applications in molecular recognition, catalysis, gas storage and separation1,2. The so-called rational design principle—synthesis of materials with predictable structures and properties—has been explored using appropriate organic molecular linkers connecting to metal nodes to control pore size and functionality of open coordination networks3,4,5,6,7,8,9. Here we demonstrate the fabrication of surface-supported MOCNs comprising tailored pore sizes and chemical functionality by the modular assembly of polytopic organic carboxylate linker molecules and iron atoms on a Cu(100) surface under ultra-high-vacuum conditions. These arrays provide versatile templates for the handling and organization of functional species at the nanoscale, as is demonstrated by their use to accommodate C60 guest molecules. Temperature-controlled studies reveal, at the single-molecule level, how pore size and chemical functionality determine the host–guest interactions.
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Davis, M.E. Ordered porous materials for emerging applications. Nature 417, 813–821 (2002).
Stein, A. Advances in microporous and mesoporous solids - highlights of recent progress. Adv. Mater. 15, 763–775 (2003).
Yaghi, O.M. et al. Reticular synthesis and the design of new materials. Nature 423, 705–714 (2003).
Fujita, M. Molecular paneling through metal-directed self-assembly. Struct. Bond. 96, 177–201 (2000).
Seo, J.S. et al. A homochiral metal-organic porous material for enantioselective separation and catalysis. Nature 404, 982–986 (2000).
Biradha, K., Hongo, Y. & Fujita, M. Open square-grid coordination polymers of the dimensions 20 × 20 Å: Remarkably stable and crystalline solids even after guest removal. Angew. Chem. Intl Edn 39, 3843–3845 (2000).
Eddaoudi, M. et al. Modular chemistry: Secondary building units as a basis for the design of highly porous and robust metal-organic carboxylate networks. Acc. Chem. Res. 34, 319–330 (2001).
Eddaoudi, M. et al. Systematic design of pore size and functionality in isoreticular MOFs and their application in methane storage. Science 295, 469–472 (2002).
Rosi, N.R. et al. Hydrogen storage in microporous metal-organic frameworks. Science 300, 1127–1129 (2003).
Dmitriev, A., Spillmann, H., Lin, N., Barth, J.V. & Kern, K. Modular assembly of two-dimensional metal-organic coordination networks at a metal surface. Angew. Chem. Intl Edn 42, 2670–2673 (2003).
Chui, S.S.-Y., Lo, S.M.-F., Charmant, J.P.H., Orpen, A.G. & Williams, I.D. A chemically functionalizable nanoporous material [Cu3(TMA)2(H2O)3]n . Science 283, 1148–1150 (1999).
Mori, W. & Takamizawa, S. Microporous materials of metal carboxylates. J. Sol. Chem. 152, 120–129 (2000).
Moulton, B., Lu, J., Hajndl, R., Hariharan, S. & Zaworotko, M.J. Crystal engineering of a nanoscale Kagomé lattice. Angew. Chem. Intl Edn 41, 2821–2824 (2002).
Maspoch, D. et al. A nanoporous molecular magnet with reversible solvent-induced mechanical and magnetic properties. Nature Mater. 2, 190–195 (2003).
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. Intl Edn 41, 4779–4783 (2002).
Messina, P. et al. Direct observation of chiral metal-organic complexes assembled on a Cu(100) surface. J. Am. Chem. Soc. 124, 14000–14001 (2002).
Lingenfelder, M. et al. Towards surface-supported supramolecular architectures: Tailored coordination assembly of 1,4-benezendicarboxylate and Fe on Cu(100). Chem. Eur. J. (in the press).
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).
Rudolf, P. in Proceedings of the International Winterschool on Electronic Properties of Novel Materials. Fullerenes and Fullerene Nanostructures (eds Kuzmany, H., Fink, J., Mehring, M. & Roth, S.) 263–275 (World Scientific, Singapore, 1996).
Hamza, A.V. in Fullerenes: Chemistry, Physics and Technology (eds Kadish, K.M. & Ruoff, R.S.) 531–554 (Wiley, New York, 2000).
Lee, K., Song, H. & Park, J.T. Fullerene - metal cluster complexes: novel bonding modes and electronic communication. Acc. Chem. Res. 36, 78–86 (2003).
Abel, M. et al. Scanning tunneling microscopy and x-ray photoelectron diffraction investigation of C60 films on Cu(100). Phys. Rev. B 67, 245407 (2003).
Fasel, R., Agostino, R.G., Aebi, P. & Schlapbach, L. Unusual molecular orientation and frozen librational motion of C60 on Cu(110). Phys. Rev. B. 60, 4517–4520 (1999).
Campbell, T.W. Dicarboxylation of terphenyl. J. Am. Chem. Soc. 82, 3126–3128 (1962).
The authors declare no competing financial interests.
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Stepanow, S., Lingenfelder, M., Dmitriev, A. et al. Steering molecular organization and host–guest interactions using two-dimensional nanoporous coordination systems. Nature Mater 3, 229–233 (2004). https://doi.org/10.1038/nmat1088
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