Intra- and Inter-Self-Assembly of Identical Supramolecules on Silver Surfaces

Abstract

Self-assembly of identical organometallic supramolecules into ordered superstructures is of great interest in both chemical science and nanotechnology due to its potential to generate neoteric properties through collective effects. In this work, we demonstrate that large-scale self-organization of atomically precise organometallic supramolecules can be achieved through cascaded on-surface chemical reactions, by the combination of intra- and inter-supramolecular interactions. Supramolecules with defined size and shape are first built through intramolecular reaction and intermolecular metal coordination, followed by the formation of well-ordered two-dimensional arrays with the assistance of Br atoms by −C–H···Br interactions. The mechanism of this process has been investigated from the perspectives of thermodynamics and kinetics.

Universal inter-molecular radical transfer reactions on metal surfaces

“…Therefore, it is intriguing to investigate the universality of surface-stabilized phenyl radical-induced dehydrogenation reactions on metal surfaces. We systematically studied the reaction behaviors of various amino/imino derivatives with/without the presence of aryl bromide precursors on Ag(111) and Cu(111), respectively 61 . For example, depositing 4-amino-p-terphenyl (APTP) on Cu(111) leads to fuzzy STM patterns, suggesting pristine APTP monomers diffuse quickly on Cu(111) at 77 K. The reaction of APTP takes place upon annealing at 370 K. In contrast, depositing 4′-bromo-1,1′-biphenyl-4-amine (BBPA) on Cu(111) at RT stimulates dehydrogenation reactions of amino groups, accompanied by the hydrogen passivation of debrominated phenyl radicals.…”