Hierarchical On-surface Synthesis of Two-dimensional Networks via Multipoint S⋯N and S⋯H bonding

Open AccessCCS ChemistryRESEARCH ARTICLES15 Mar 2024Hierarchical On-surface Synthesis of Two-dimensional Networks via Multipoint S⋯N and S⋯H bonding Chen-Hui Shu, Li-Xia Kang, Shan-shan Wang, Yan He, Ruo-Xi Zhang, Xuelei Su, Ping Yu, Xingguang Li and Pei-Nian Liu Chen-Hui Shu , Li-Xia Kang , Shan-shan Wang , Yan He , Ruo-Xi Zhang , Xuelei Su , Ping Yu , Xingguang Li and Pei-Nian Liu https://doi.org/10.31635/ccschem.024.202303820 SectionsSupplemental MaterialAboutPDF ToolsAdd to favoritesDownload CitationsTrack Citations ShareFacebookTwitterLinked InEmail Although electrostatic bonding between chalcogen atoms and nitrogen has emerged as a powerful driving force in the fabrication of supramolecular structures, this noncovalent bond has not yet been used to link polymers to form networks. Taking advantage of additive enthalpy in forming multipoint noncovalent bonds, in this study we constructed a two-dimensional (2D) network via the hierarchical on-surface synthesis of linear polymer chains followed by multipoint S⋯N and S⋯H bonding. When 4,7-dibromobenzo[c][1,2,5]thiadiazole was used, only short oligomers with embedded bromine atoms and cross-linked byproducts were formed on Ag(111) or Au(111) surfaces after multiple annealing procedures, and no 2D network was observed. By changing the precursor to a similar iodine-substituted molecule, long linear polymers were generated and assembled with iodine atoms on Au(111) after annealing at 523 K. After annealing to 603 K, iodine atoms were desorbed and polymer chains were assembled via multipoint noncovalent bonding. The 2D network remained intact after annealing to 653 K, demonstrating its high thermostability. The multipoint noncovalent bonds were investigated by the combination of scanning tunneling microscopy, non-contact atomic force microscopy, and density functional theory calculations, which revealed that S⋯N and S⋯H bonding are the driving forces to construct thermostable and orderly 2D networks. Download figure Download PowerPoint Previous articleNext article FiguresReferencesRelatedDetails Issue AssignmentNot Yet AssignedSupporting Information Copyright & Permissions© 2024 Chinese Chemical Society Downloaded 0 times PDF downloadLoading ...