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Supramolecular coordination self-assembly on the solid surface offers great possibilities for creating nanostructures and thin films with unique physicochemical properties. In this work, we present a simple lattice model based on competitive coordination motifs that enables predictions of the phase behavior and thermal stability of metal–organic networks consisting of 1,3,5-tris(pyridyl)benzene (TPyB) and transition metals on the Au(111) surface. The main parameter of the model is the ratio between the energies of the two-fold and three-fold metal–ligand coordination defined by the type of the metal center. The model reveals a homologous series of flower phases that differ in the metal/ligand composition. Existing ranges of the phases in terms of the chemical potential (or partial pressure) of the components are determined by the mentioned ratio. The closer the value of this parameter is to unity, the more diverse is …