Monte Carlo simulation of the surface-assisted self-assembly of metal-organic precursors comprising phenanthrene building blocks

Abstract

Surface-assisted fabrication of carbon-based covalent architectures has been a promising pathway to low-dimensional materials with special physicochemical properties and functions. In this contribution, the Monte Carlo simulation method was used to predict the formation of metal-organic precursors preceding the covalent Ullmann coupling of halogenated phenanthrene monomers. To that end, the coarse-grained model of adsorbing (111) surface, phenanthrene molecules and linking adatoms was proposed, in which the monomers were equipped with active centers providing directional metal-linker interactions. The simulations performed for various intramolecular distributions of active centers in the phenanthrene unit (corresponding to halogen positions) resulted in diverse metal-organic superstructures, including chains, ring oligomers, triangular and windmill trimers, ladders, and periodic and aperiodic networks. For those molecules which were chiral in 2D the corresponding calculations in enantiopure and racemic overlayers were also carried out. These simulations resulted in characteristic examples of both advantageous and adverse effect of the opposite enantiomer on the ordering in racemic systems. Our theoretical findings provided some hints on how to halogenate monomeric phenanthrene units to create polymeric architectures with presumed structural features, such as topology, periodicity, connectivity, ramification and porosity.