Article | Published:

Controlling on-surface polymerization by hierarchical and substrate-directed growth

Nature Chemistry volume 4, pages 215220 (2012) | Download Citation

Abstract

A key challenge in the field of nanotechnology, in particular in the design of molecular machines, novel materials or molecular electronics, is the bottom-up construction of covalently bound molecular architectures in a well-defined arrangement. To date, only rather simple structures have been obtained because of the limitation of one-step connection processes. Indeed, for the formation of sophisticated structures, step-by-step connection of molecules is required. Here, we present a strategy for the covalent connection of molecules in a hierarchical manner by the selective and sequential activation of specific sites, thereby generating species with a programmed reactivity. This approach leads to improved network quality and enables the fabrication of heterogeneous architectures with high selectivity. Furthermore, substrate-directed growth and a preferred orientation of the molecular nanostructures are achieved on an anisotropic surface. The demonstrated control over reactivity and diffusion during covalent bond formation constitutes a promising route towards the creation of sophisticated multi-component molecular nanostructures.

  • Compound C45H36Br2

    α,ω-Dibromoter(9,9'-dimethyl)fluorene

  • Compound C44H26Br4N4

    5,10,15,20-Tetrakis(4'-bromophenyl)porphyrin

  • Compound C44H26Br2I2N4

    5,15-Bis(4'-bromophenyl)-10,20-bis(4'-iodophenyl)porphyrin

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Acknowledgements

This work was funded by the Deutsche Forschungsgemeinschaft (DFG) through SFB 658 and European Projects ARTIST and AtMol. Funding from Fondo Trieste, MIUR (PRIN2008), CNR (NOMCIS) and the EU (NFFA) is gratefully acknowledged by the Trieste group.

Author information

Author notes

    • F. Esch

    Present address: Chemistry Department, Technische Universität München, 85748 Garching, Germany

Affiliations

  1. Department of Physical Chemistry, Fritz-Haber-Institute of the Max-Planck-Society, 14195 Berlin, Germany

    • L. Lafferentz
    •  & L. Grill
  2. Department of Chemistry, Humboldt-Universität zu Berlin, 12489 Berlin, Germany

    • V. Eberhardt
    •  & S. Hecht
  3. IOM-CNR Laboratorio TASC, Area Science Park, 34149 Basovizza-Trieste, Italy

    • L. Lafferentz
    • , C. Dri
    • , C. Africh
    • , G. Comelli
    •  & F. Esch
  4. Physics Department and CENMAT, University of Trieste, 34127 Trieste, Italy

    • G. Comelli

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Contributions

S.H. and L.G. conceived the experiments. V.E. and S.H. synthesized the molecules. L.L., C.D., C.A., G.C., F.E. and L.G. performed the experiments. L.L., C.D. and L.G. analysed the data and L.G. wrote the paper. All authors discussed the results and commented on the manuscript.

Competing interests

The authors declare no competing financial interests.

Corresponding authors

Correspondence to S. Hecht or L. Grill.

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DOI

https://doi.org/10.1038/nchem.1242

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