Extended Two-Dimensional Metal–Organic Frameworks Based on Thiolate–Copper Coordination Bonds

Self-assembly and surface-mediated reactions of 1,3,5-tris(4-mercaptophenyl)benzenea three-fold symmetric aromatic trithiolare studied on Cu(111) by means of scanning tunneling microscopy (STM) under ultrahigh-vacuum (UHV) conditions. In order to reveal the nature of intermolecular bonds and to understand the specific role of the substrate for their formation, these studies were extended to Ag(111). Room-temperature deposition onto either substrate yields densely packed trigonal structures with similar appearance and lattice parameters. Yet, thermal annealing reveals distinct differences between both substrates: on Cu(111) moderate annealing temperatures (∼150 °C) already drive the emergence of two different porous networks, whereas on Ag(111) higher annealing temperatures (up to ∼300 °C) were required to induce structural changes. In the latter case only disordered structures with characteristic dimers were observed. These differences are rationalized by the contribution of the adatom gas on Cu(111) to the formation of metal-coordination bonds. Density functional theory (DFT) methods were applied to identify intermolecular bonds in both cases by means of their bond distances and geometries.