Towards Surface-Supported Supramolecular Architectures: Tailored Coordination Assembly of 1,4-Benzenedicarboxylate and Fe on Cu(100)

We present a comprehensive investigation of the modular assembly of surface‐supported metal–organic coordination systems with specific topologies and high structural stability formed by vapor deposition of 1,4‐benzenedicarboxylic acid molecules and iron atoms on a Cu(100) surface under ultra‐high vacuum conditions. By making use of the two carboxylate moieties available for lateral linkage to Fe atoms, we succeeded in the fabrication of distinct Fe–carboxylate coordination architectures at the surface by carefully adjusting the ligand and metal concentration ratio and the temperature of the post‐deposition annealing treatment. The mononuclear, 1D‐polymeric and fully 2D‐reticulated metallosupramolecular arrangements obtained were characterized in situ at the single‐molecule level by scanning tunneling microscopy. Metallosupramolecular chemistry conducted at a surface. The assembly of a series of low‐dimensional coordination architectures was achieved by vapor deposition of Fe atoms and organic ligands under ultra‐high vacuum conditions. The topology and stoichiometry are controlled by constituent concentration and annealing parameters. The images show the single‐molecule resolution topography obtained in situ by scanning tunneling microscopy. Fe atoms engaged in iron‐carboxylate bonds are highlighted by gray spheres.