Article Supramolecular Polymorphism of the Hydrogen-Bonded C3-Symmetrical Hexadehydrotribenzo[12]annulene Derivative

Yotaro Kasahara ; Takashi Takeda ORCID ; Shun Dekura ORCID ; Yoshiki Ishii ORCID ; Hayato Anetai ; Atsuro Takai SAMURAI ORCID ; Ichiro Hisaki ORCID ; Masayuki Takeuchi SAMURAI ORCID ; Tomoyuki Akutagawa ORCID

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Yotaro Kasahara, Takashi Takeda, Shun Dekura, Yoshiki Ishii, Hayato Anetai, Atsuro Takai, Ichiro Hisaki, Masayuki Takeuchi, Tomoyuki Akutagawa. Supramolecular Polymorphism of the Hydrogen-Bonded C3-Symmetrical Hexadehydrotribenzo[12]annulene Derivative. Journal of the American Chemical Society. 2025, 147 (22), 18783-18795. https://doi.org/10.1021/jacs.5c02529

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(abstract)

C3-symmetric hexadehydrotribenzo[12]annulene ([12]DBA) derivative with three tetradecylamide chains capable of hydrogen-bonding interaction formed either a two-dimensional lamellar (LM) or a one-dimensional (1D) nanofiber (NF) molecular assemblies, depending on the association state of the amide hydrogen bonds in
solution phase. The intermolecular amide hydrogen-bonding modes in the LM and NF structures were different from each other. The NF structure was metastable less stable than the LM structure, and was obtained through organogel formation. In chloroform, the [12]DBA derivative exhibited 1D association behavior following the isodesmic model due to intermolecular amide hydrogen bonds, whereas the presence of acetonitrile inhibited this association state. The NF structure had larger amplitude dynamics about the polar amide group than that of the LM structure, undergoing a phase transition from the NF to the LM structures upon heating. The absorption spectra of the NF and the solid state LM were different from each other, exhibiting a different optical properties. The coexistence of intermolecular amide hydrogen bonds and van der Waals interactions among the C3-symmetric molecules resulted in polymorphic phenomena, where energetically similar molecular assemblies were expressed.

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Keyword: Polymorphism, Supramolecular Assembly

Date published: 2025-06-04

Publisher: American Chemical Society (ACS)

Journal:

  • Journal of the American Chemical Society (ISSN: 00027863) vol. 147 issue. 22 p. 18783-18795

Funding:

  • University Fellowship Creation Project for Creating Scientific and Technological Innovation JPMJFS2102
  • ACT-X JPMJAX23D3
  • ACT-X JPMJAX23DF
  • Japan Society for the Promotion of Science JP20H05865
  • Japan Society for the Promotion of Science JP23K13715
  • Japan Society for the Promotion of Science JP24H01727
  • Japan Society for the Promotion of Science JP24K01452
  • Support for Pioneering Research Initiated by the Next Generation JPMJSP2114
  • Izumi Science and Technology Foundation

Manuscript type: Publisher's version (Version of record)

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First published URL: https://doi.org/10.1021/jacs.5c02529

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Updated at: 2025-06-16 12:30:39 +0900

Published on MDR: 2025-06-16 12:23:41 +0900

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