Theoretical Modeling of the Metal‐Organic Precursors of Anthracene‐Based Covalent Networks on Surfaces

Surface‐assisted fabrication of molecular network architectures has been a promising route to low‐dimensional materials with unique physicochemical properties and functionalities. One versatile way in this field is the Ullmann coupling reaction of halogenated organic monomers on catalytically active metallic surfaces. In this work, using the coarse‐grained Monte Carlo simulations, we studied the on‐surface self‐assembly of metal‐organic precursors preceding the covalent Ullman‐type linkage of tetrahalogenated anthracene building blocks. To that end, a series of positional isomers was examined and classified with respect to their ability of creation of extended network structures. Our simulations focused on the identification of basic types of self‐assembly scenarios distinguishing enantiopure and racemic systems and producing periodic and aperiodic networks. The calculations carried out for selected tectons demonstrated wide possibilities of controlling porosity (e. g. pore size, shape, periodicity, chirality, heterogeneity) of the networks by suitable functionalization of the monomeric unit. The findings reported herein can be helpful in rational designing of 2D polymeric networks with predefined structures and properties. Diverse 2D metal‐organic networks comprising tetrahalogenated naphthalene building blocks were predicted using the coarse‐grained Monte Carlo simulations. Modeling of these structures being precursors of covalently bonded polymers on surfaces provided insight into the relation between intramolecular distribution of halogen substituents in the monomer and architecture of the resulting networks.