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On-surface synthesis has become a powerful technique for obtaining various nanostructures, mainly by linking small precursor molecules. In contrast, the cleavage of specific moieties from precursor molecules is also an important and promising strategy to increase the variety of products. Here, we report the on-surface synthesis of hexabenzocoronene (HBC) and its hexa-fluorinated analogue (6F-HBC) from the parent heptaphenylcycloheptatrienes, via the systematic extrusion of a phenyl-CH: carbenic fragment and a subsequent cyclodehydrogenation process on a Au(111) substrate. Their structures and electronic properties were investigated in-depth by low-temperature scanning tunneling microscopy with a CO-terminated tip. Annealing at 200 °C triggers the elimination of the phenylcarbenic groups from the cycloheptatriene core, resulting in the formation of both hexaphenylbenzene and its fluorinated analogue. Although the former was transformed into HBC via cyclodehydrogenation at 300 °C, the fluorinated one was thermally desorbed from the surface even at 250 °C. We found that depositing fluorinated heptaphenylcycloheptatriene onto the substrate kept at 300 °C successfully yielded 6F-HBC. The influence of fluorine substitution was identified through molecular assemblies and bond-resolved images as well as dI/dV measurements, all obtained using the same CO-terminated tip. Our findings demonstrate that the retro-Büchner reaction, corresponding to a ring contraction, is an effective strategy to enhance the variety of structures and electronic properties of on-surface synthesized products.

権利情報:

• Creative Commons BY Attribution 4.0 International
  

キーワード: Scanning probe microscopy, On-surface synthesis, Hexabenzocoronene, Retro-Büchner reaction, Heptaarylcycloheptatrienes, Surface-assisted chemical reactions

刊行年月日: 2026-10-22

出版者: American Chemical Society (ACS)

掲載誌:

• The Journal of PhysicalChemistry Letters (ISSN: 19487185) vol. 17 issue. 42 p. 12171-12178

研究助成金:

• Japan Society for the Promotion of Science 22H00325
• Japan Society for the Promotion of Science 24KF0269
• Japan Society for the Promotion of Science 25H00422
• Japan Society for the Promotion of Science 25K24715
• Japan Society for the Promotion of Science JP25KJ1768
• Centre National de la Recherche Scientifique (International Research Project POEMES (2024−2028))
• National Institute for Materials Science (Internship program (for P.P.))
• Ministry of Education, Culture, Sports, Science and Technology JPMXP1224NR5041 (ARIM Program)
• Ministry of Education, Culture, Sports, Science and Technology JPMXP1225NR5016 (ARIM Program)
• The framework of the “Programme des Investissements d’Avenir” ANR-17-EURE-0009 (Grant NanoX, Université de Toulouse)

原稿種別: 出版者版 (Version of record)

MDR DOI:

公開URL: https://doi.org/10.1021/acs.jpclett.6c01675

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更新時刻: 2026-10-29 13:28:58 +0900

MDRでの公開時刻: 2026-10-29 14:29:41 +0900