Department of Chemistry, The University of Tokyo, Hongo 7-3-1, Bunkyo-ku, Tokyo, 113-0033, Japan.
Chem Asian J. 2023 Apr 17;18(8):e202300046. doi: 10.1002/asia.202300046. Epub 2023 Mar 20.
Molecular hyperboloids were designed and synthesized. The synthesis was achieved by development of oligomeric macrocyclization of an octagonal molecule with a saddle shape. The saddle-shaped molecule, that is, [8]cyclo-meta-phenylene ([8]CMP), was decorated with two linkers for the oligomeric macrocyclization and was synthetically assembled by Ni-mediated Yamamoto coupling. Three congeners of the molecular hyperboloids (2mer-4mer) were obtained, and 2mer and 3mer were subjected to X-ray crystallographic analysis. Crystal structures revealed nanometer-sized hyperboloidal structures with 96π and 144π electrons, which also possessed nanopores on the curved molecular structures. Structures of [8]CMP cores of the molecular hyperboloids were compared with those of saddle-shaped phenine [8]circulene with a negative Gauss curvature to confirm their structural resemblance, which suggests further explorations of expanded networks of molecular hyperboloids.
设计并合成了分子双曲面体。通过具有鞍形的八元分子的齐聚物大环化反应来实现合成。鞍形分子，即[8]环-间-亚苯基([8]CMP)，用两个连接体进行齐聚物大环化反应进行修饰，并通过 Ni 介导的 Yamamoto 偶联进行合成组装。得到了三种分子双曲面体的同系物（2mer-4mer），并对 2mer 和 3mer 进行了 X 射线晶体结构分析。晶体结构揭示了具有 96π 和 144π 电子的纳米级双曲面体结构，这些结构在弯曲的分子结构上还具有纳米孔。对分子双曲面体[8]CMP 核的结构与具有负高斯曲率的鞍形菲[8]轮烯的结构进行了比较，以确认它们的结构相似性，这表明可以进一步探索分子双曲面体的扩展网络。
