Order–Disorder Transition of Two-Dimensional Molecular Networks through a Stoichiometric Design

Materials with disordered structures may exhibit interesting properties. Metal-organic frameworks (MOFs) are a class of hybrid materials composed of metal nodes and coordinating organic linkers. Recently, there has been growing interest in MOFs with structural disorder and the investigations of amorphous structures on surfaces. Herein, we demonstrate a bottom-up method to construct disordered molecular networks on metal surfaces by selecting two organic molecule linkers with the same symmetry but different sizes for preparing two-component samples with different stoichiometric ratios. The amorphous networks are directly imaged by scanning tunneling microscopy under ultrahigh vacuum with a submolecular resolution, allowing us to quantify its degree of disorder and other structural properties. Furthermore, we resort to molecular dynamics simulations to understand the formation of the amorphous metal-organic networks. The results may advance our understanding of the mechanism of formation of monolayer molecular networks with structural disorders, facilitating the design and exploration of amorphous MOF materials with intriguing properties.