Two-dimensional polymer formation on surfaces: insight into the roles of precursor mobility and reactivity

A combined scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS), and density functional theory (DFT) is used for studying the surface-assisted assembly of the hexaiodo-substituted macrocycle cyclohexa-m-phenylene (CHP) toward covalently bonded polyphenylene networks on Cu(111), Au(111) and Ag(111) surfaces. Monte Carlo simulation has shown that different balances between diffusion and intermolecular coupling have determined the branched and compact polyphenylene networks on the Cu and Ag surface, which has shown that the choice of the substrate has played a vital role in the formation of two-dimensional polymers.