Skip to main content

Thank you for visiting You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

Functionalizing hydrogen-bonded surface networks with self-assembled monolayers


One of the central challenges in nanotechnology is the development of flexible and efficient methods for creating ordered structures with nanometre precision over an extended length scale. Supramolecular self-assembly on surfaces offers attractive features in this regard: it is a ‘bottom-up’ approach and thus allows the simple and rapid creation of surface assemblies1,2, which are readily tuned through the choice of molecular building blocks used and stabilized by hydrogen bonding3,4,5,6,7,8, van der Waals interactions9, π–π bonding10,11 or metal coordination12,13 between the blocks. Assemblies in the form of two-dimensional open networks3,9,10,13,14,15,16,17 are of particular interest for possible applications because well-defined pores can be used for the precise localization and confinement of guest entities such as molecules or clusters, which can add functionality to the supramolecular network. Another widely used method for producing surface structures involves self-assembled monolayers (SAMs)18, which have introduced unprecedented flexibility in our ability to tailor interfaces and generate patterned surfaces19,20,21,22. But SAMs are part of a top-down technology that is limited in terms of the spatial resolution that can be achieved. We therefore rationalized that a particularly powerful fabrication platform might be realized by combining non-covalent self-assembly of porous networks and SAMs, with the former providing nanometre-scale precision and the latter allowing versatile functionalization. Here we show that the two strategies can indeed be combined to create integrated network–SAM hybrid systems that are sufficiently robust for further processing. We show that the supramolecular network and the SAM can both be deposited from solution, which should enable the widespread and flexible use of this combined fabrication method.

This is a preview of subscription content, access via your institution

Relevant articles

Open Access articles citing this article.

Access options

Buy article

Get time limited or full article access on ReadCube.


All prices are NET prices.

Figure 1: Supramolecular network of melamine-PTCDI self-assembled on Au(111).
Figure 2: Generation of a network–SAM hybrid structure.
Figure 3: UPD of Cu on Au(111) modified by an adamantane-thiol-filled PTCDI–melamine network.


  1. De Feyter, S. & De Schryver, F. C. Two-dimensional supramolecular self-assembly probed by scanning tunneling microscopy. Chem. Soc. Rev. 32, 139–150 (2003)

    Article  CAS  Google Scholar 

  2. Barth, J. V. Molecular architectonic on metal surfaces. Annu. Rev. Phys. Chem. 58, 375–407 (2007)

    Article  ADS  CAS  Google Scholar 

  3. 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)

    Article  ADS  CAS  Google Scholar 

  4. Li, Z., Han, B., Wan, L. J. & Wandlowski, T. Supramolecular nanostructures of 1,3,5-benzene-tricarboxylic acid at electrified Au(111)/0.05 M H2SO4 interfaces: An in situ scanning tunneling microscopy study. Langmuir 21, 6915–6928 (2005)

    Article  CAS  Google Scholar 

  5. Pinheiro, L. S. & Temperini, M. L. A. Pyridine and pyridine carboxylic acids as guests in a bidimensional hydrogen bond structure analyzed by scanning tunneling microscopy. Surf. Sci. 601, 1836–1843 (2007)

    Article  ADS  CAS  Google Scholar 

  6. Canas-Ventura, M. E. et al. Self-assembly of periodic bicomponent wires and ribbons. Angew. Chem. Int. Ed. 46, 1814–1818 (2007)

    Article  CAS  Google Scholar 

  7. Payer, D. et al. Ionic hydrogen bonds controlling two-dimensional supramolecular systems at a metal surface. Chem. Eur. J. 13, 3900–3906 (2007)

    Article  CAS  Google Scholar 

  8. Kampschulte, L., Griessl, S., Heckl, W. M. & Lackinger, M. Mediated coadsorption at the liquid–solid interface: Stabilization through hydrogen bonds. J. Phys. Chem. B 109, 14074–14078 (2005)

    Article  CAS  Google Scholar 

  9. Furukawa, S. et al. Structural transformation of a two-dimensional molecular network in response to selective guest inclusion. Angew. Chem. Int. Ed. 46, 2831–2834 (2007)

    Article  CAS  Google Scholar 

  10. Mena-Osteritz, E. & Bäuerle, P. Complexation of C60 on a cyclothiophene monolayer template. Adv. Mater. 18, 447–451 (2006)

    Article  CAS  Google Scholar 

  11. Schenning, A. & Meijer, E. W. Supramolecular electronics; nanowires from self-assembled π-conjugated systems. Chem. Commun. 3245–3258 (2005)

  12. Diaz, D. J., Bernhard, S., Storrier, G. D. & Abruna, H. D. Redox active ordered arrays via metal initiated self-assembly of terpyridine based ligands. J. Phys. Chem. B 105, 8746–8754 (2001)

    Article  CAS  Google Scholar 

  13. Stepanow, S. et al. Steering molecular organization and host–guest interactions using two-dimensional nanoporous coordination systems. Nature Mater. 3, 229–233 (2004)

    Article  ADS  CAS  Google Scholar 

  14. Stöhr, M., Wahl, M., Spillmann, H., Gade, L. H. & Jung, T. A. Lateral manipulation for the positioning of molecular guests within the confinements of a highly stable self-assembled organic surface network. Small 3, 1336–1340 (2007)

    Article  Google Scholar 

  15. 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)

    Article  CAS  Google Scholar 

  16. Lu, J. et al. Template-induced inclusion structures with copper(II) phthalocyanine and coronene as guests in two-dimensional hydrogen-bonded host networks. J. Phys. Chem. B 108, 5161–5165 (2004)

    Article  CAS  Google Scholar 

  17. Stepanow, S. et al. Surface-assisted assembly of 2D metal-organic networks that exhibit unusual threefold coordination symmetry. Angew. Chem. Int. Ed. 46, 710–713 (2007)

    Article  CAS  Google Scholar 

  18. Schreiber, F. Self-assembled monolayers: from ‘simple’ model systems to biofunctionalized interfaces. J. Phys. Condens. Matter 16, R881–R900 (2004)

    Article  ADS  CAS  Google Scholar 

  19. Gooding, J. J., Mearns, F., Yang, W. R. & Liu, J. Q. Self-assembled monolayers into the 21st century: Recent advances and applications. Electroanal. 15, 81–96 (2003)

    Article  CAS  Google Scholar 

  20. Mrksich, M. A surface chemistry approach to studying cell adhesion. Chem. Soc. Rev. 29, 267–273 (2000)

    Article  CAS  Google Scholar 

  21. Thom, I., Hähner, G. & Buck, M. Replicative generation of metal microstructures by template directed electrometallization. Appl. Phys. Lett. 87, 024101 (2005)

    Article  ADS  Google Scholar 

  22. Love, J. C., Estroff, L. A., Kriebel, J. K., Nuzzo, R. G. & Whitesides, G. M. Self-assembled monolayers of thiolates on metals as a form of nanotechnology. Chem. Rev. 105, 1103–1170 (2005)

    Article  CAS  Google Scholar 

  23. Perdigao, L. M. A. et al. Bimolecular networks and supramolecular traps on Au(111). J. Phys. Chem. B 110, 12539–12542 (2006)

    Article  CAS  Google Scholar 

  24. Weber, U. K. et al. Role of interaction anisotropy in the formation and stability of molecular templates. Phys. Rev. Lett. 100, 156101– (2008)

    Article  ADS  CAS  Google Scholar 

  25. Aakeroy, C. B. & Seddon, K. R. The hydrogen-bond and crystal engineering. Chem. Soc. Rev. 22, 397–407 (1993)

    Article  CAS  Google Scholar 

  26. Baldacchini, C., Mariani, C. & Betti, M. G. Adsorption of pentacene on filled d-band metal surfaces: Long-range ordering and adsorption energy. J. Chem. Phys. 124, 154702 (2006)

    Article  ADS  Google Scholar 

  27. Bilic, A., Reimers, J. R., Hush, N. S., Hoft, R. C. & Ford, M. J. Adsorption of benzene on copper, silver, and gold surfaces. J. Chem. Theory Comput. 2, 1093–1105 (2006)

    Article  CAS  Google Scholar 

  28. Dameron, A. A., Charles, L. F. & Weiss, P. S. Structures and displacement of 1-adamantanethiol self-assembled monolayers on Au{111}. J. Am. Chem. Soc. 127, 8697–8704 (2005)

    Article  CAS  Google Scholar 

  29. Silien, C. & Buck, M. On the role of extrinsic and intrinsic defects in the underpotential deposition of Cu on thiol-modified Au(111) electrodes. J. Phys. Chem. C 112, 3881–3890 (2008)

    Article  CAS  Google Scholar 

  30. Oyamatsu, D., Kanemoto, H., Kuwabata, S. & Yoneyama, H. Nanopore preparation in self-assembled monolayers of alkanethiols with use of the selective desorption technique assisted by underpotential deposition of silver and copper. J. Electroanal. Chem. 497, 97–105 (2001)

    Article  CAS  Google Scholar 

Download references


We are grateful to J. D. E. T. Wilton-Ely for his contribution to the synthesis of BP3SH. This work was supported by the UK Engineering Physical Sciences Research Council (EPSRC). M.R. acknowledges support from the Academy of Finland.

Author Contributions All authors contributed to the design of the experiments. The preparation and characterization of networks and hybrid systems were performed by R.M and M.T.R.. Experiments and analysis related to electrochemistry were conducted by C.S. All authors contributed to the manuscript, with M.B. and R.M. leading.

Author information

Authors and Affiliations


Corresponding authors

Correspondence to Rafael Madueno or Manfred Buck.

PowerPoint slides

Rights and permissions

Reprints and Permissions

About this article

Cite this article

Madueno, R., Räisänen, M., Silien, C. et al. Functionalizing hydrogen-bonded surface networks with self-assembled monolayers. Nature 454, 618–621 (2008).

Download citation

  • Received:

  • Accepted:

  • Issue Date:

  • DOI:

This article is cited by


By submitting a comment you agree to abide by our Terms and Community Guidelines. If you find something abusive or that does not comply with our terms or guidelines please flag it as inappropriate.


Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing