Interfacial supramolecular self-assembly represents a powerful tool for constructing regular and quasicrystalline materials. In particular, complex two-dimensional molecular tessellations, such as semi-regular Archimedean tilings with regular polygons, promise unique properties related to their nontrivial structures. However, their formation is challenging, because current methods are largely limited to the direct assembly of precursors, that is, where structure formation relies on molecular interactions without using chemical transformations. Here, we have chosen ethynyl-iodophenanthrene (which features dissymmetry in both geometry and reactivity) as a single starting precursor to generate the rare semi-regular (18.104.22.168) Archimedean tiling with long-range order on an atomically flat substrate through a multi-step reaction. Intriguingly, the individual chemical transformations converge to form a symmetric alkynyl–Ag–alkynyl complex as the new tecton in high yields. Using a combination of microscopy and X-ray spectroscopy tools, as well as computational modelling, we show that in situ generated catalytic Ag complexes mediate the tecton conversion.
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The authors acknowledge funding by the German Research Foundation (DFG) Excellence Cluster Munich Center for Advanced Photonics, DFG project KL 2294/3–1 and ERC Advanced Grant MolArt (no. 247299). M.R. acknowledges support by the DFG-priority programs 1459, TR88 ‘3Met’ and the KNMF facility (KIT, Germany). The authors thank the Helmholtz–Zentrum Berlin–Electron storage ring BESSY II for provision of synchrotron radiation at beamline HE-SGM and thank C. Wöll and A. Nefedov for providing access to the HE-SGM end station.
The authors declare no competing financial interests.
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Zhang, YQ., Paszkiewicz, M., Du, P. et al. Complex supramolecular interfacial tessellation through convergent multi-step reaction of a dissymmetric simple organic precursor. Nature Chem 10, 296–304 (2018). https://doi.org/10.1038/nchem.2924
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