, Volume 76, Issue 5, pp 645-652

Supramolecular architectures and nanostructures at metal surfaces

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The controlled formation of non-covalent bonds (H-bonding, metal–ligand interactions) is the key ingredient for the fabrication of supramolecular architectures and nanostructures. Upon deposition of molecular building blocks at well-defined surfaces, this issue can be directly addressed. Scanning tunneling microscopy observations are presented, which provide insight into the interaction of functional groups on metal substrates at the molecular level. In particular, carboxylic acids were employed: (4-[(pyrid-4-yl-ethynyl)]-benzoic acid (PEBA), 4-[trans-2-(pyrid-4-yl-vinyl)]-benzoic acid (PVBA) and trimesic acid (1,3,5-benzenetricarboxylic acid, TMA), which could be stabilized in a flat geometry at the surface. By choosing the appropriate substrate material and symmetry, the sensitive balance of intermolecular and molecule–substrate interactions can be tuned to obtain well-defined supramolecular architectures and nanostructures. The head-to-tail hydrogen bonding of the related rod-like species PEBA and PVBA stabilizes molecular rows on Ag(111). The subtle difference in the molecular geometries is reflected in the lateral ordering: While 2-D islanding is encountered with PEBA, 1-D nanogratings of supramolecular chiral H-bonded twin chains evolve for PVBA. The threefold symmetry of TMA in conjunction with the self-complementarity of its exodentate groups accounts for the formation of H-bonded honeycomb networks on Cu(100) at low temperatures. Metal–ligand interactions were probed with PVBA and TMA at Cu surfaces at ambient temperature. Deprotonation of the carboxyl moiety takes place, which readily interacts with Cu adatoms evaporated from step edges. This leads to a head-to-head pairing of PVBA on Cu(111) and cloverleaf-shaped Cu–TMA coordination compounds on Cu(001).