First-principles study of chalcogen-bonded self-assembly structures on silicene: Some insight into the fabrication of molecular architectures on surfaces through chalcogen bonding

Abstract

In this work, the self-assembly structures of a set of chalcogenazolo and chalcogendiazolo derivatives on silicene surface were studied in detail using first-principles DFT calculations, with the aim of providing fundamental insight into the fabrication of supramolecular architectures on surfaces through chalcogen bonding (ChB). The adsorption behaviors of single molecules on the facet were firstly investigated and, subsequently, the dimeric and trimeric complexes consisting of different self-assembled patterns, such as wire-, ribbon- and herringbone-like structures, were examined either in gas phase or on the surface. The assemblies of these molecules are driven by not only intermolecular Ch∙∙∙N bonds but also vdW interactions between the molecules and the substrate. Intermolecular Te∙∙∙N contacts appear to be the primary interactions in the self-assembly systems, although the Te-congeners show an enhanced affinity on the surface. In contrast, intermolecular S∙∙∙N contacts are somewhat weaker with comparable strength to interfacial interactions with the substrate.