Lattice-Driven Formation of a Two-Dimensional Organometallic Network Containing Both Phenyl-Ag-N and Phenyl-Ag-Phenyl...

Metal-organic frameworks (MOFs) have garnered significant interest due to their broad structural, chemical, and functional tunability. On-surface synthesis has emerged as a facile method for constructing two-dimensional (2D) MOFs, wherein the substrate not only supplies metal atoms as coordination centers but also facilitates the activation of chemical bonds to prepare organometallic networks. However, most organometallic networks fabricated through this approach so far are composed of a single type of node, and building organometallic networks with multiple distinct nodes remains challenging. Here, we report the on-surface synthesis of a 2D binodal organometallic network composed of both phenyl-Ag-N and phenyl-Ag-phenyl nodes via the on-surface reaction of a bifunctional precursor 3,3",6,6"-tetrabromo-9,9'-bicarbazole on Ag(110). High-resolution scanning tunneling microscopy is employed to unravel the complex surface reaction process on the molecular scale. Combined growth mechanism analysis and density functional theory calculations reveal that the formation of the ordered 2D binodal organometallic network is driven by its commensurability with the underlying Ag(110) lattice. The present work underscores the essential role of substrate-adsorbate lattice matching in the synthesis of complex and ordered surface-supported nanostructures.