The realization of complex long-range ordered structures in a Euclidean plane presents a significant challenge en route to the utilization of their unique physical and chemical properties. Recent progress in on-surface supramolecular chemistry has enabled the engineering of regular and semi-regular tilings, expressing translation symmetric, quasicrystalline, and fractal geometries. However, the k-uniform tilings possessing several distinct vertices remain largely unexplored. Here, we show that these complex geometries can be prepared from a simple bitopic molecular precursor - 4,4'-biphenyl dicarboxylic acid (BDA) - by its controlled chemical transformation on the Ag(001) surface. The realization of 2- and 3-uniform tilings is enabled by partially carboxylated BDA mediating the seamless connection of two distinct binding motifs in a single long-range ordered molecular phase. These results define the basic self-assembly criteria, opening way to the utilization of complex supramolecular tilings.

CEITEC Central European Institute of Technology Brno University of Technology Purkyňova 123 612 00 Brno Czech Republic

Institute of Physical Engineering Brno University of Technology Technická 2896 2 616 69 Brno Czech Republic

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Complex k-uniform tilings by a simple bitopic precursor self-assembled on Ag(001) surface