Empowering non-covalent hydrogen, halogen, and [S–N]2 bonds in synergistic molecular assemblies on Au(111). Issue 48 (2nd December 2022)

• Record Type: Journal Article
• Authors: Barragán, Ana; Lois, Sara; Sarasola, Ane; Vitali, Lucia
• Is Part Of: Nanoscale. Volume 14:Issue 48(2022)
• Page Start: 17895
• Page End: 17899
• Publication Date: 2022-12-02
• Subjects: Nanoscience -- Periodicals; Nanotechnology -- Periodicals; 620.505
• DOI: 10.1039/d2nr05984c
• Languages: English
• ISSNs: 2040-3364

Abstract

Abstract : We describe the synergistic assembly of two molecular networks through non-covalent bonds. These interactions are fundamental for designing self-assembled organic structures with potentially high responsiveness to mechanical, light, and thermal stimuli. Abstract : 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-dibromobenzo[ c ]-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–N]2 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.