Kasahara Yotaro, Takeda Takashi, Dekura Shun, Ishii Yoshiki, Anetai Hayato, Takai Atsuro, Hisaki Ichiro, Takeuchi Masayuki, Akutagawa Tomoyuki
Graduate School of Engineering, Tohoku University, Sendai 980-8579, Japan.
Institute of Multidisciplinary Research for Advanced Materials (IMRAM), Tohoku University, 2-1-1 Katahira, Aoba-ku, Sendai 980-8577, Japan.
J Am Chem Soc. 2025 Jun 4;147(22):18783-18795. doi: 10.1021/jacs.5c02529. Epub 2025 May 25.
The -symmetric hexadehydrotribenzo[12]annulene () derivative () with three tetradecylamide (-NHCOCH) chains capable of hydrogen-bonding interaction formed either a two-dimensional lamellar () or a one-dimensional (1D) nanofiber () molecular assembly, depending on the association state of the amide hydrogen bonds in the solution phase. The intermolecular amide hydrogen-bonding modes in the and structures were different from each other. The structure was metastable, 2.2 kJ mol less stable than that of the structure, and was obtained through organogel formation. In CHCl, exhibited a 1D association behavior following the isodesmic model ( = 2.18 × 10 M) due to intermolecular amide hydrogen bonds, whereas the presence of CHCN inhibited this association state. The structure had larger amplitude dynamics about the polar amide group than that of the structure, undergoing a phase transition from the to the structure upon heating. The absorption spectra of and solid-state were different from each other, exhibiting different optical properties. The coexistence of intermolecular amide hydrogen bonds and van der Waals interactions among the -symmetric molecules resulted in polymorphic phenomena, where energetically similar molecular assemblies were expressed.
具有三条能够形成氢键相互作用的十四烷基酰胺（-NHCOCH）链的对称六脱氢三亚苯并[12]轮烯（）衍生物（），根据溶液相中酰胺氢键的缔合状态，形成二维层状（）或一维（1D）纳米纤维（）分子聚集体。和结构中的分子间酰胺氢键模式彼此不同。结构是亚稳态的，比结构的稳定性低2.2 kJ/mol，并且是通过有机凝胶形成获得的。在CHCl中，由于分子间酰胺氢键，表现出遵循等键模型（= 2.18×10 M）的一维缔合行为，而CHCN的存在抑制了这种缔合状态。结构中极性酰胺基团的动力学振幅比结构的大，加热时会发生从结构到结构的相变。和固态的吸收光谱彼此不同，表现出不同的光学性质。对称分子间分子间酰胺氢键和范德华相互作用的共存导致了多晶型现象，其中表达了能量上相似的分子聚集体。
