# On-Surface Synthesisof Hexabenzocoronenes via a Retro-BüchnerReaction of Heptaarylcycloheptatrienes

https://mdr.nims.go.jp/datasets/fd83ff08-4d2c-4541-82b4-5c0180942b13

## File

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## Id

fd83ff08-4d2c-4541-82b4-5c0180942b13

## Local identifier



## Visibility

open_to_public

## State

published

## Created at

2026-10-29T02:08:54.779023Z

## Updated at

2026-10-29T04:28:58.264181Z

## Published at

2026-10-29T05:29:41.620926Z

## Doi



## First published url

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

## Date published

2026-10-22

## Recorded date published

2026-10-22

## Resource type

journal_article

## Manuscript type

vor

## Collection



## Title

- title: On-Surface Synthesisof Hexabenzocoronenes via a Retro-BüchnerReaction of
    Heptaarylcycloheptatrienes
  title_type: original
  lang: en

## Description

- description: '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.'
  description_type: abstract
  lang: en

## Creator

- name: Shigeki Kawai
  role: author
  orcid: https://orcid.org/0000-0003-2128-0120
  organization: National Institute for Materials Science
- name: Haruka Tsuji
  role: author
  orcid: https://orcid.org/0009-0007-9218-719X
  organization: National Institute for Materials Science
- name: Donglin Li
  role: author
  orcid: https://orcid.org/0009-0001-6866-8715
  organization: National Institute for Materials Science
- name: Pranshu Pal
  role: author
  organization: National Institute of Technology Srinagar
- name: Oscar Custance
  role: author
  orcid: https://orcid.org/0000-0001-7931-603X
  organization: National Institute for Materials Science
- name: Toshikaze Kariyado
  role: author
  orcid: https://orcid.org/0000-0002-3746-6803
  organization: National Institute for Materials Science
- name: Yorie Ohno
  role: author
  organization: Nara Institute of Science and Technology
- name: Yohei Hattori
  role: author
  organization: Nara Institute of Science and Technology
- name: Thomas A. Hector
  role: author
  organization: Université de Toulouse,
- name: Claire Kammerer
  role: author
  organization: Université de Toulouse,
- name: Gwénaël Rapenne
  role: author
  organization: Nara Institute of Science and Technology

## Contact agent



## Publisher

organization: American Chemical Society (ACS)

## Managing organization



## Keyword

- subject: Scanning probe microscopy
  schema: not_defined
- subject: On-surface synthesis
  schema: not_defined
- subject: Hexabenzocoronene
  schema: not_defined
- subject: Retro-Büchner reaction
  schema: not_defined
- subject: Heptaarylcycloheptatrienes
  schema: not_defined
- subject: Surface-assisted chemical reactions
  schema: not_defined

## Rights

- identifier: https://creativecommons.org/licenses/by/4.0/
  date_licensed: 2026-08-25

## Other identifier(s)



## Data origin

- data_origin_type: other

## Embargo



## Journal

- title: The Journal of PhysicalChemistry Letters
  issn: '19487185'
  volume: '17'
  issue: '42'
  start_page: 12171
  end_page: 12178

## Conference



## Related item



## Funding

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

## Instrument



## Instrument operator



## Instrument managing organization



## Measurement method



## Specimen



## Chemical composition



## Structure for specimen



## Structural feature for specimen



## Specific property for specimen



## Process for specimen treatment



## Computational method



## Energy level/transition state



## Software



## Custom property



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