Role of the Structure and Reactivity of Cu and Ag Surfaces in the Formation of a 2D Metal-Hexahydroxytriphenylene Network

Abstract

We have investigated the role played by the atomic structure and reactivity of the supporting Ag(111) and Cu(111) surfaces on the formation of 2D metal-organic networks (2D-MONs) involving metal adatom clusters spawned by these two surfaces. While the hexahydroxytriphenylene (HHTP) molecule forms complexes with Ag3 and Cu3 adatom clusters on, respectively, the Ag(111) and Cu(111) surfaces, an extended order is only observed in the 2D-MON on Ag(111). By combining scanning tunneling microscopy measurements, density functional theory calculations, and microscopy image simulations, we show that the formation of Ag-HHTP metal-organic complexes is structurally compatible with a periodic arrangement of HHTP on the Ag(111) surface. In contrast, on Cu(111), tightly bonded and localized Cu-HHTP motifs are stabilized by the interaction of Cu adclusters with HHTP. However, they cannot match the surface structure of Cu(111) to form an extended 2D-MON. We observed that the formation of large 2D-MON domains on a metallic surface is only possible when the periodicity of the adsorbed surface assembly is weakly perturbed by the addition of metal adclusters that reinforced the bonding.