Empowering non-covalent hydrogen, halogen, and S–N2 bonds in synergistic molecular assemblies on Au(111)

摘要

Non-covalent bonds are fundamental for designing self-assembled organic structures with potentially high responsiveness to mechanical, light, and thermal stimuli. The weak intermolecular interaction allows triggering charge-transport, energy-conversion, enzymatic, and catalytic activity, to name a few. Here, we discuss the synergistic action that multiple highly-directional and purely electrostatic bonds have in assembling one molecular specie, namely 4,7-dibromobenzoc-1,2,5-thiadiazole (2Br-BTD), in two different patterns on the Au(111) surface. We find, using scanning tunneling microscopy (STM) and density functional theory (DFT), that multiple secondary-interactions strengthen the electrostatic attraction between the pnicogen and chalcogen atoms forming S–N2 heterocycles, the building block of the two networks. Among these interactions, there are halogen–halogen bonds that form characteristic supra-molecular synthons of 3, 4, or 6 molecules. However, not all these nodal structures contribute to the cohesion of the system. In such cases, other secondary bonds involving hydrogen or nitrogen compensate for the eventual deficiency.