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


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.

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Figure 1: Molecular building blocks with bromine and iodine substituents for sequential activation.
Figure 2: Hierarchical growth following sequential thermal activation.
Figure 3: Size distribution for non-hierarchical and hierarchical growth.
Figure 4: Heterogeneous structures by hierarchical growth.
Figure 5: Controlling covalent linking through substrate orientation.
Figure 6: Copolymerization and segregation on a Au(100) surface.


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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.

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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.

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Correspondence to S. Hecht or L. Grill.

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The authors declare no competing financial interests.

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Lafferentz, L., Eberhardt, V., Dri, C. et al. Controlling on-surface polymerization by hierarchical and substrate-directed growth. Nature Chem 4, 215–220 (2012).

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