Matsuno Taisuke, Ohtomo Yutaro, Someya Maki, Isobe Hiroyuki
Department of Chemistry, The University of Tokyo, Bunkyo-ku, Tokyo, Japan.
Nat Commun. 2021 Mar 10;12(1):1575. doi: 10.1038/s41467-021-21889-8.
The periodicity of two-dimensional entities can be manipulated by their stacking assembly, and incommensurate stacks of bilayers are attracting considerable interest in materials science. Stereoisomerism in incommensurate bilayers was first noted with incommensurate double-wall carbon nanotubes composed of helical carbon networks, but the lack of structural information hampered the chemical understanding such as the stereoselectivity during bilayer formation. In this study, we construct a finite molecular version of incommensurate carbon bilayers by assembling two helical cylindrical molecules in solution. An outer cylindrical molecule is designed to encapsulate a small-bore helical cylindrical molecule, and the spontaneous assembly of coaxial complexes proceeds in a stereoselective manner in solution with a preference for heterohelical combinations over diastereomeric, homohelical combinations. The rational design of incommensurate bilayers for material applications may be facilitated by the design and development of molecular versions with discrete structures with atomic precision.
二维实体的周期性可以通过它们的堆叠组装来操控，并且双层的非 commensurate 堆叠在材料科学中引起了相当大的兴趣。非 commensurate 双层中的立体异构现象最初是在由螺旋碳网络组成的非 commensurate 双壁碳纳米管中被发现的，但是缺乏结构信息阻碍了对诸如双层形成过程中的立体选择性等化学现象的理解。在本研究中，我们通过在溶液中组装两个螺旋圆柱形分子构建了非 commensurate 碳双层的有限分子版本。一个外部圆柱形分子被设计用来包裹一个小口径螺旋圆柱形分子，并且同轴配合物的自发组装在溶液中以立体选择性的方式进行，相比于非对映体、同螺旋组合，更倾向于异螺旋组合。具有原子精度的离散结构的分子版本的设计和开发可能有助于为材料应用合理设计非 commensurate 双层。
