4.8 Article

Figure-eight thermal hysteresis of aminomethylenehelicene oligomers with terminal C16 alkyl groups during hetero-double-helix formation

Journal

CHEMICAL SCIENCE
Volume 11, Issue 12, Pages 3290-3300

Publisher

ROYAL SOC CHEMISTRY
DOI: 10.1039/c9sc06496f

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Funding

  1. Japan Society for the Promotion of Science (JSPS) [17H03050, 17H08203]
  2. JSPS [18J10706]
  3. Grants-in-Aid for Scientific Research [18J10706] Funding Source: KAKEN

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1 : 1 mixtures of aminomethylenehelicene (P)-tetramer and (M)-pentamer with terminal C-16 alkyl groups in fluorobenzene showed structural changes between hetero-double-helices B and C and random-coils 2A. Figure-eight thermal hysteresis appeared when the solution was cooled and heated at a constant rate and involved the crossing of cooling and heating curves in Delta epsilon/temperature profiles. This unusual thermal hysteresis emerged in the intermediate state between counterclockwise and clockwise thermal hystereses. This phenomenon arose from the competition between self-catalytic reactions to form B and C from 2A. Significant effects of terminal C-16 alkyl groups on the thermodynamic and kinetic phenomena are also described.

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