The on-surface synthesis of organic polymers has been recently recognized as a useful method to create lowdimensional covalently bonded structures with tailorable topology and functions. In this work, the Monte Carlo simulation method was used to study the metal−organic precursors of covalent polymers formed in the Ullmann-type coupling reaction of halogenated naphthalene derivatives. To this purpose, a coarsegrained model was proposed in which the monomers, represented by a pair of interconnected segments, and two-coordinate metal atoms (one segment) were adsorbed on a triangular latticemimicking (111) catalytically active crystalline surface. Different distributions of halogen atoms in the naphthalene molecules were modeled using the directional interactions assigned to these units, sustaining the resulting metal−tecton reversible links. Depending on the halogen content and distribution, the simulations predicted the creation of diverse supramolecular connections such as linear and cyclic aggregates and other more complex forms. Moreover, in the case of prochiral monomers, the calculations demonstrated basic structural differences between the enantiopure and racemic assemblies in which chiral separation or mixing was observed. The obtained results can be helpful in directing the surface-assisted polymerization reactions toward organic structures with predefined size, shape, symmetry, and connectivity.

Functionalized polycyclic aromatic hydrocarbons (PAHs) have been recently recognized as promising building blocks for surface-assisted polymerization reactions producing low-dimensional covalent structures with tailorable properties. In this work, we used the lattice Monte Carlo (MC) simulation method to predict the structure of the labile metal−(halogenated)anthracene connections preceding the formation of covalent polymers in the Ullmann-type coupling reaction occurring on catalytically active metallic surfaces. To that purpose, a coarse-grained model of mono-, di-, and trisubstituted anthracene monomers and two-coordinate metal atoms was proposed, in which these components were adsorbed on a triangular lattice. The formation of metal−organic nodes cementing the resulting superstructures was assumed to be dependent on the directionality of the short-range interactions assigned differently to PAH molecules. Our extensive MC simulations performed for the complete set of 50 positional isomers predicted various organometallic intermediates with morphologies ranging from cyclic oligomers, chains, ladders, ribbons to aperiodic networks and others. These results were compared with the analogous findings obtained for the smaller naphthalene unit. The outcome of the theoretical studies reported herein can be helpful in designing low-dimensional covalent polymers with tunable architecture and functions.

Organic synthesis reactions in adsorbed phase have been recently an intensively studied topic in heterogeneous catalysis and material engineering. One of such processes is the Ullmann coupling in which halogenated...

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.