Exfoliatable Layered 2D Honeycomb Crystals of Host‐guest Complexes Networked by CH‐π Hydrogen Bonds

• Published in: Angewandte Chemie International Edition 2024-08, Vol.63 (34), p.e202406502-n/a
• Main Authors: Terasaki, Seiya, Kotani, Yuki, Katsuno, Ryosuke, Matsuno, Taisuke, Fukunaga, Toshiya M., Ikemoto, Koki, Isobe, Hiroyuki
• Format: Article
• Language: English
• Subjects: Apexes; Atomic structure; Bonding strength; Chemical bonds; Covalent bonds; Crystal structure; Crystals; Graphene; honeycomb structure; Hydrogen bonding; Hydrogen bonds; nanotubes; Stereochemistry; supramolecular chemistry; Two dimensional materials; two-dimensional crystals
• ISSN: 1433-7851; 1521-3773; 1521-3773
• DOI: 10.1002/anie.202406502

Studies of graphene show that robust chemical bonds such as covalent bonds with trigonal‐planar atoms afford layered atomic 2D crystals possessing unique properties. Although layered molecular crystals are of interest to diversify elements and structures of 2D materials, the structural diversity of molecules as well as weak intermolecular interactions inevitably makes the design to be one‐off and individual. We herein report a versatile method to assemble layered molecular crystals. By developing a D3‐symmetry host at vertices to form a honeycomb layer, a diverse range of layered 2D host–guest crystals were obtained. Substituents on the host, elements/structures of the guest, the stereochemistry of the host and types of intercalants were diversified, which should allow for 6×32×3×2 combinations for structural diversification. A cylindrical molecule with D3‐symmetry was found to serve as versatile vertices to form 2‐dimensional, honeycomb networks of host–guest complexes. Varying the structural elements of the layered systems enabled a wide range of structural combinations to become accessible.