Cyclodehydrogenation of molecular nanographene precursors catalyzed by atomic hydrogen

• Published in: Nature communications 2025-01, Vol.16 (1), p.691-10, Article 691
• Main Authors: Zuzak, Rafal, Dabczynski, Pawel, Castro-Esteban, Jesús, Martínez, José Ignacio, Engelund, Mads, Pérez, Dolores, Peña, Diego, Godlewski, Szymon
• Format: Article
• Language: English
• Subjects: 119/118; 140/58; 147/136; 147/138; 147/3; 639/301/357; 639/638/542; 639/925/357; Catalysts; Chemical reactions; Chemical synthesis; Chemical-mechanical polishing; Germanium; Gold; Graphene; Humanities and Social Sciences; Hydrogen; Insulators; Magnetic semiconductors; Magnetic structure; Metals; multidisciplinary; Nanostructure; Optoelectronic devices; Science; Science (multidisciplinary); Semiconductors; Silicon dioxide; Sodium chloride; Substrates; Surface reactions; Thin films; Titanium dioxide
• ISSN: 2041-1723; 2041-1723
• DOI: 10.1038/s41467-024-54774-1

Atomically precise synthesis of graphene nanostructures on semiconductors and insulators has been a formidable challenge. In particular, the metallic substrates needed to catalyze cyclodehydrogenative planarization reactions limit subsequent applications that exploit the electronic and/or magnetic structure of graphene derivatives. Here, we introduce a protocol in which an on-surface reaction is initiated and carried out regardless of the substrate type. We demonstrate that, counterintuitively, atomic hydrogen can play the role of a catalyst in the cyclodehydrogenative planarization reaction. The high efficiency of the method is demonstrated by the nanographene synthesis on metallic Au, semiconducting TiO 2 , Ge:H, as well as on inert and insulating Si/SiO 2 and thin NaCl layers. The hydrogen-catalyzed cyclodehydrogenation reaction reported here leads towards the integration of graphene derivatives in optoelectronic devices as well as developing the field of on-surface synthesis by means of catalytic transformations. It also inspires merging of atomically shaped graphene-based nanostructures with low-dimensional inorganic units into functional devices. On-surface synthesis of nanographenes proceeds differently on metals than on semiconductors or insulating substrates. Here, the authors perform substrate type-independent chemistry with atomic hydrogen acting as a catalyst in the intramolecular cyclodehydrogenation reaction of polyarenes, yielding atomically precise nanographenes.