On-surface Ullmann coupling of halo-derivatives of arenes: Monte Carlo simulations for tetracene

Abstract

On-surface synthesis of C-C covalent low-dimensional nanomaterials is a promising method of obtaining structures with tailored and novel physicochemical and electric properties. In this contribution, the Monte Carlo simulation approach was proposed to predict the topology of metal-organic (MO) intermediates formed in the Ullmann homocoupling of halogenated isomers of tetracene. The coarse-grained model of polyaromatic hydrocarbons (PAH) haloderivatives and divalent copper adatoms on a metallic crystal surface (111) was used, where locations of substituents in the molecules were encoded as active centres with directional C-Cu interactions. The computations were performed for various structural isomers of tetracene, from disubstituted to tetrasubstituted units. As a result, diverse superstructures were obtained, such as dimers, trimers, and other oligomers, chains and ladders, and metal-organic networks, both chiral and achiral. Additionally, for the prochiral linkers, simulations of the racemic mixtures were performed. Our study provided useful insight into the influence of substituents’ position and the carbon backbone’s size on the topology of the modelled precursor architectures.