Constructing Molecular Networks on Metal Surfaces through Tellurium-Based Chalcogen-Organic Interaction.

Abstract

On-surface molecular self-assembly presents an important approach to the development of low-dimensional functional nanostructures and nanomaterials. Traditional strategies primarily exploit hydrogen bonding or metal coordination, yet the potential of chalcogen bonding (ChB) for on-surface self-assemblies remains underexplored. Here, we explore fabricating molecular networks via tellurium (Te)-directed chalcogen-organic interactions. Employing carbonitrile molecules as molecular building blocks, we have achieved extended 2D networks exhibiting a 4-fold binding motif on Au(111), marking a notable difference from the conventional coordinative interaction involving transition metals. Our findings, supported by density functional theory (DFT) and scanning tunneling spectroscopy (STS), show that the Te-carbonitrile interaction exhibits lower stability compared to the metal-organic coordination, and the construction of the Te-directed molecular networks does not alter the electronic properties of the involved molecules. Introducing chalcogen-directed interactions may expand the spectrum of strategies in supramolecular assembly, contributing to the design of advanced molecular architectures for nanotechnological applications.