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Cycloparaphenylene–Phenalenyl Radical and Its Dimeric Double Nanohoop


Yang, Yong; Blacque, Olivier; Sato, Sota; Juríček, Michal (2021). Cycloparaphenylene–Phenalenyl Radical and Its Dimeric Double Nanohoop. Angewandte Chemie Internationale Edition, 60(24):13529-13535.

Abstract

A neutral open-shell carbon nanoring was achieved by integration of the phenalenyl unit into the cycloparaphenylene framework. It is shown that the spin distribution and reactivity of this hydrocarbon in the shape of a diamond ring are a result of steric and electronic effects and that selective dimerization yields a double nanohoop with a radial-planar-radial arrangement of its three π-conjugated segments comprising a total of 158 sp2-carbon atoms.
The first example of a neutral spin-delocalized carbon-nanoring radical was achieved by integration of the open-shell phenalenyl unit into cycloparaphenylene (CPP). Spin distribution in this hydrocarbon is localized primarily on the phenalenyl segment and partially on the CPP segment as a consequence of steric and electronic effects. The resulting geometry is reminiscent of a diamond ring, with pseudo-perpendicular arrangement of the radial and the planar π-surface. The phenylene rings attached directly to the phenalenyl unit give rise to a steric effect that governs a highly selective dimerization pathway, yielding a giant double nanohoop. Its π-framework made of 158 sp2-carbon atoms was elucidated by single-crystal X-ray diffraction, which revealed a three-segment CPP-peropyrene-CPP structure. This nanocarbon shows a fluorescence profile characteristic of peropyrene, regardless of which segment gets excited. These results in conjunction with DFT suggest that adjusting the size of the CPP segments in this double nanohoop could deliver donor–acceptor systems.

Abstract

A neutral open-shell carbon nanoring was achieved by integration of the phenalenyl unit into the cycloparaphenylene framework. It is shown that the spin distribution and reactivity of this hydrocarbon in the shape of a diamond ring are a result of steric and electronic effects and that selective dimerization yields a double nanohoop with a radial-planar-radial arrangement of its three π-conjugated segments comprising a total of 158 sp2-carbon atoms.
The first example of a neutral spin-delocalized carbon-nanoring radical was achieved by integration of the open-shell phenalenyl unit into cycloparaphenylene (CPP). Spin distribution in this hydrocarbon is localized primarily on the phenalenyl segment and partially on the CPP segment as a consequence of steric and electronic effects. The resulting geometry is reminiscent of a diamond ring, with pseudo-perpendicular arrangement of the radial and the planar π-surface. The phenylene rings attached directly to the phenalenyl unit give rise to a steric effect that governs a highly selective dimerization pathway, yielding a giant double nanohoop. Its π-framework made of 158 sp2-carbon atoms was elucidated by single-crystal X-ray diffraction, which revealed a three-segment CPP-peropyrene-CPP structure. This nanocarbon shows a fluorescence profile characteristic of peropyrene, regardless of which segment gets excited. These results in conjunction with DFT suggest that adjusting the size of the CPP segments in this double nanohoop could deliver donor–acceptor systems.

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Additional indexing

Item Type:Journal Article, refereed, further contribution
Communities & Collections:07 Faculty of Science > Department of Chemistry
Dewey Decimal Classification:540 Chemistry
Scopus Subject Areas:Physical Sciences > Catalysis
Physical Sciences > General Chemistry
Uncontrolled Keywords:General Chemistry, Catalysis
Language:English
Date:7 June 2021
Deposited On:13 Jan 2022 14:26
Last Modified:26 Feb 2024 02:42
Publisher:Wiley-VCH Verlag
ISSN:1433-7851
OA Status:Hybrid
Free access at:Publisher DOI. An embargo period may apply.
Publisher DOI:https://doi.org/10.1002/anie.202101792
Project Information:
  • : FunderSNSF
  • : Grant IDPP00P2_170534
  • : Project TitleControl of Spin Interactions in Helical Systems
  • Content: Published Version
  • Licence: Creative Commons: Attribution-NonCommercial-NoDerivatives 4.0 International (CC BY-NC-ND 4.0)