title: Crystalline Graphdiyne Nanosheets Produced at a Gas/Liquid or Liquid/Liquid Interface.
abstract: Synthetic two-dimensional polymers, or bottom-up nanosheets, are ultrathin polymeric frameworks with in-plane periodicity. They can be synthesized in a direct, bottom-up fashion using atomic, ionic, or molecular components. However, few are based on carbon-carbon bond formation, which means that there is a potential new field of investigation into these fundamentally important chemical bonds. Here, we describe the bottom-up synthesis of all-carbon, π-conjugated graphdiyne nanosheets. A liquid/liquid interfacial protocol involves layering a dichloromethane solution of hexaethynylbenzene on an aqueous layer containing a copper catalyst at room temperature. A multilayer graphdiyne (thickness, 24 nm; domain size, >25 μm) emerges through a successive alkyne-alkyne homocoupling reaction at the interface. A gas/liquid interfacial synthesis is more successful. Sprinkling a very small amount of hexaethynylbenzene in a mixture of dichloromethane and toluene onto the surface of the aqueous phase at room temperature generated single-crystalline graphdiyne nanosheets, which feature regular hexagonal domains, a lower degree of oxygenation, and uniform thickness (3.0 nm) and lateral size (1.5 μm).
authors.affiliation: Department of Chemistry, Graduate School of Science, The University of Tokyo , 7-3-1, Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.|Japan Society for the Promotion of Science (JSPS), Ichibancho, Chiyoda-ku, Tokyo 102-8471, Japan.
authors.forename: Ryota
authors.initials: R
authors.lastname: Matsuoka
authors.affiliation: Department of Chemistry, Graduate School of Science, The University of Tokyo , 7-3-1, Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.|JST-PRESTO, 4-1-8, Honcho, Kawaguchi, Saitama 332-0012, Japan.
authors.forename: Ryota
authors.identifier: 0000-0002-8702-1378
authors.initials: R
authors.lastname: Sakamoto
authors.affiliation: Department of Chemistry, Graduate School of Science, The University of Tokyo , 7-3-1, Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.
authors.forename: Ken
authors.initials: K
authors.lastname: Hoshiko
authors.affiliation: Faculty of Fiber Science and Engineering, Kyoto Institute of Technology ,Matsugasaki Hashikami-cho 1, Sakyo-ku, Kyoto 606-8585, Japan.|RIKEN SPring-8 Center, Hyogo 679-5148, Japan.
authors.forename: Sono
authors.initials: S
authors.lastname: Sasaki
authors.affiliation: Japan Synchrotron Radiation Research Institute (JASRI)/SPring-8, 1-1-1 Kouto, Sayo-cho, Sayo-gun, Hyogo 679-5198, Japan.
authors.forename: Hiroyasu
authors.initials: H
authors.lastname: Masunaga
authors.affiliation: JST-PRESTO, 4-1-8, Honcho, Kawaguchi, Saitama 332-0012, Japan.|Department of Materials Engineering, The University of Tokyo , Tokyo 113-8656, Japan.
authors.forename: Kosuke
authors.initials: K
authors.lastname: Nagashio
authors.affiliation: Department of Chemistry, Graduate School of Science, The University of Tokyo , 7-3-1, Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.
authors.forename: Hiroshi
authors.initials: H
authors.lastname: Nishihara