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.

The Flexible On-Surface Self-Assembly of a Low-Symmetry Mabiq Ligand: An Unconventional Metal-Assisted Phase Transformation on Ag(111)

“…While not all the recorded STM images reveal the silver adatoms as clearly discernible features in the HT network (Figure and Figure S6); nevertheless, the evidence provided in Figure and Figure S7 is indicative of a stabilizing N-Ag interaction. Furthermore, it seems a general feature of the Ag adatoms that they tend to be poorly visible, thus elusive, in the STM imaging, as inferred from previous reports. − Numerous examples highlight the adatom-induced formation of surface-confined metal-coordination networks, in particular for nitrogen-containing pyridine derivatives. − Strikingly, in recent synthetic studies in solution (Supporting Information, Section 10), we also observed the formation of trimetallic Mabiq dimers linked via a central silver atom that bridges two adjoining biquinazoline moieties (Figure S13). This finding provides important evidence for the affinity of the peripheral H-Mabiq site for Ag coordination and the capacity of this metal to bridge two Mabiq units.…”

“…The ball-and-stick model presented in Figure and overlaid on the STM image shows that this cavity provides sufficient space to accommodate the Ag adatoms. Indeed, the occurrence of thermally triggered incorporation of Ag adatoms into supramolecular organic networks was recently reported. − The presence of Ag adatoms would justify the unusual arrangement of two bulky diketiminate units facing each other, imaged as bright four-lobed protrusions in STM. In contrast, for the RT phase, while similarly large cavities are observed in the self-assembly (Figure a and the tentative ball-and-stick model in Figure S8), we found no STM evidence of adatom incorporation at varying bias.…”

Periodic DFTB for Supported Clusters: Implementation and Application on Benzene Dimers Deposited on Graphene

“…The modeling of functional extended surfaces has grown in past decades to investigate, for fundamental and engineering purposes, a large number of phenomena or applications such as, e.g., deposition [1], growth and migration [2], 2D assembly [3], catalysis [4], electrocatalysis [5], photocatalysis [6], molecular electronics [7], depollution [8], sensing [9], etc. Many of these studies have focused on deposited clusters, i.e., finite aggregations of basis elements (atoms or molecules) adsorbed on surfaces.…”

Transformation of the coordination nanostructures of 4,4′,4′′-(1,3,5-triazine-2,4,6-triyl) tribenzoic acid molecules on HOPG triggered by the change in the concentration of metal ions

“…A variety of studies have demonstrated the coordination nanostructures by altering organic ligands, such as carboxylate, 3,5,12,18 hydroxyl, 14,20,21 pyridine, 9,22–25 and triazine. 26–30 The triazine derivatives are important in a range of areas as ligands for supramolecular self-assembly of more complex mixed layers, hence it may be interesting to study the coordination properties of the triazine derivatives.…”