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On‐Surface Assembly of Hydrogen‐ and Halogen‐Bonded Supramolecular Graphyne‐Like Networks

Zechao Yang, Lukas Fromm, Tim Sander, Julian Gebhardt, Tobias A. Schaub, Andreas Görling, Milan Kivala, Sabine Maier

2020Angewandte Chemie International Edition35 citationsDOIOpen Access PDF

Abstract

Abstract Demonstrated here is a supramolecular approach to fabricate highly ordered monolayered hydrogen‐ and halogen‐bonded graphyne‐like two‐dimensional (2D) materials from triethynyltriazine derivatives on Au(111) and Ag(111). The 2D networks are stabilized by N⋅⋅⋅H−C(sp) bonds and N⋅⋅⋅Br−C(sp) bonds to the triazine core. The structural properties and the binding energies of the supramolecular graphynes have been investigated by scanning tunneling microscopy in combination with density‐functional theory calculations. It is revealed that the N⋅⋅⋅Br−C(sp) bonds lead to significantly stronger bonded networks compared to the hydrogen‐bonded networks. A systematic analysis of the binding energies of triethynyltriazine and triethynylbenzene derivatives further demonstrates that the X 3 ‐synthon, which is commonly observed for bromobenzene derivatives, is weaker than the X 6 ‐synthon for our bromotriethynyl derivatives.

Topics & Concepts

SynthonGraphyneSupramolecular chemistryHydrogen bondHalogen bondHalogenCrystallographyScanning tunneling microscopeDensity functional theoryTriazineMaterials scienceChemistryNanotechnologyMoleculeComputational chemistryStereochemistryPolymer chemistryOrganic chemistryCrystal structureAlkylSurface Chemistry and CatalysisGraphene research and applicationsTopological Materials and Phenomena