Surface Chemistry of a Halogenated Borazine: From Supramolecular Assemblies to a Random Covalent BN-Substituted Carbon Network

The on-surface synthesis strategy has emerged as a promising route for fabricating well-defined two-dimensional (2D) BN-substituted carbon nanomaterials with tunable electronic properties. This approach relies on specially designed precursors and requires a thorough understanding of the on-surface r...

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Published inChemistry : a European journal p. e202402492
Main Authors Tömekce, Birce Sena, Cuxart, Marc G, Caputo, Laura, Poletto, Daniele, Charlier, Jean-Christophe, Bonifazi, Davide, Auwärter, Willi
Format Journal Article
LanguageEnglish
Published Germany 07.09.2024
Subjects
surface chemistry
BNC structure
covalent network
borazine
nanostructures
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Summary:The on-surface synthesis strategy has emerged as a promising route for fabricating well-defined two-dimensional (2D) BN-substituted carbon nanomaterials with tunable electronic properties. This approach relies on specially designed precursors and requires a thorough understanding of the on-surface reaction pathways. It promises precise structural control at the atomic scale, thus complementing chemical vapor deposition (CVD). In this study, we investigated a novel heteroatomic precursor, tetrabromoborazine, which incorporates a BN core and an OH group, on Ag(111) using low temperature scanning tunnelling microscopy/spectroscopy (LT-STM/STS) and X-ray photoelectron spectroscopy (XPS). Through sequential temperature-induced reactions involving dehalogenation and dehydrogenation, distinct tetrabromoborazine derivatives were produced as reaction intermediates, leading to the formation of specific self-assemblies. Notably, the resulting intricate supramolecular structures include a chiral kagomé lattice composed of molecular dimers exhibiting a unique electronic signature. The final product obtained was a random covalent carbon network with BN-substitution and embedded oxygen heteroatoms. Our study offers valuable insights into the significance of the structure and functionalization of BN precursors in temperature-induced on-surface reactions, which can help future rational precursor design. Additionally, it introduces complex surface architectures that offer a high areal density of borazine cores.
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ISSN:0947-6539
1521-3765
1521-3765
DOI:10.1002/chem.202402492