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Random two-dimensional string networks based on divergent coordination assembly

Nature Chemistry volume 2, pages 131–137 (2010)Cite this article

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Abstract

The bulk properties of glasses and amorphous materials have been studied widely, but the determination of their structural details at the molecular level is hindered by the lack of long-range order. Recently, two-dimensional, supramolecular random networks were assembled on surfaces, and the identification of elementary structural motifs and defects has provided insights into the intriguing nature of disordered materials. So far, however, such networks have been obtained with homomolecular hydrogen-bonded systems of limited stability. Here we explore robust, disordered coordination networks that incorporate transition-metal centres. Cobalt atoms were co-deposited on metal surfaces with a ditopic linker that is nonlinear, prochiral (deconvoluted in three stereoisomers on two-dimensional confinement) and bears terminal carbonitrile groups. In situ scanning tunnelling microscopy revealed the formation of a set of coordination nodes of similar energy that drives a divergent assembly scenario. The expressed string formation and bifurcation motifs result in a random reticulation of the entire surface.

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Figure 1: Deconvolution of the prochiral molecular linker [1,1′;4′,1′′]-terphenyl-3,3′′-dicarbonitrile on 2D confinement.
Figure 2: STM images of random coordination string networks.
Figure 3: Molecular-resolution STM images of a disordered coordination network on Ag(111).
Figure 4: Random coordination string networks on Ag(111).
Figure 5: Molecular manipulation experiments.

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Acknowledgements

Dedicated to Professor Jean-Marie Lehn on the occasion of his 70th birthday. Work supported by the European Science Foundation Collaborative Research Programme FunSMARTs, the DFG Cluster of Excellence Munich Center for Advanced Photonics (MAP), DFG Centre of Functional Nanostructures Karlsruhe (project CFN E3.5), the Canadian Natural Sciences and Engineering Research Council and the Canada Foundation for Innovation. We thank U. Schlickum, I. Silanes and A. Arnau for helpful discussions and providing additional information.

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Authors and Affiliations

  1. Physik Department E20, TU München, James-Franck Strasse, Garching, D-85748, Germany

    Matthias Marschall, Joachim Reichert, Knud Seufert, Willi Auwärter & Johannes V. Barth

  2. Department of Physics & Astronomy, University of British Columbia, Vancouver, 2355 East Mall, Vancouver, V6T 1Z4, Canada

    Matthias Marschall, Joachim Reichert, Alexander Weber-Bargioni & Johannes V. Barth

  3. Institut für Nanotechnologie, Karlsruhe Institute of Technology, Karlsruhe, D-76021, Germany

    Svetlana Klyatskaya, Giorgio Zoppellaro & Mario Ruben

  4. IPCMS-CNRS UMR 7504, Université de Strasbourg, 23 Rue du Loess, Strasbourg, 67034, France

    Mario Ruben

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Contributions

M.M., J.R., A.W.-B., K.S. and W.A. performed the experiments, and analysed and interpreted the data. S.K. and G.Z. developed the synthesis of the linkers used. J.V.B. and M.R. conceived the studies and co-wrote the paper with W.A., M.M. and J.R.

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Correspondence to Mario Ruben or Johannes V. Barth.

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Marschall, M., Reichert, J., Weber-Bargioni, A. et al. Random two-dimensional string networks based on divergent coordination assembly. Nature Chem 2, 131–137 (2010). https://doi.org/10.1038/nchem.503

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