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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.

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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.


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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.

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Correspondence to Rafael Madueno or Manfred Buck.

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

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