title: D3h -Symmetric Porphyrin-Based Rigid Macrocyclic Ligands for Multicofacial Multinuclear Complexes in a One-Nanometer-Sized Cavity.
abstract: The one-step synthesis of D3h -symmetric cyclic porphyrin trimers 1 composed of three 2,2'-[4,4'-bis(methoxycarbonyl)]bipyridyl moieties and three porphyrinatozinc moieties was achieved from a nickel-mediated reductive coupling of meso-5,15-bis(6-chloro-4-methoxycarbonylpyrid-2-yl)porphyrinatozinc. Although cyclic trimers 1 were obtained as a mixture that included other cyclic and acyclic porphyrin oligomers, an extremely specific separation was observed only for cyclic trimers 1 when using columns of silica gel modified with pyrenylethyl, cyanopropyl, and other groups. Structural analysis of cyclic trimers 1 was carried out by means of NMR spectroscopy and X-ray crystallography. Treatment of an η(3) -allylpalladium complex with a cyclic trimer gave a tris(palladium) complex containing three η(3) -allylpalladium groups inside the space, which indicated that the bipyridyl moieties inside the ring could work as bidentate metalloligands.
authors.affiliation: Graduate School of Chemical Sciences and Technology, Tokyo University of Science, 1-3 Kagurazaka, Shinjuku-ku, Tokyo 162-8601 (Japan).
authors.forename: Yohei
authors.initials: Y
authors.lastname: Ohkoda
authors.affiliation: Graduate School of Chemical Sciences and Technology, Tokyo University of Science, 1-3 Kagurazaka, Shinjuku-ku, Tokyo 162-8601 (Japan).
authors.forename: Akane
authors.initials: A
authors.lastname: Asaishi
authors.affiliation: Graduate School of Chemical Sciences and Technology, Tokyo University of Science, 1-3 Kagurazaka, Shinjuku-ku, Tokyo 162-8601 (Japan).
authors.forename: Tomoya
authors.initials: T
authors.lastname: Namiki
authors.affiliation: Graduate School of Chemical Sciences and Technology, Tokyo University of Science, 1-3 Kagurazaka, Shinjuku-ku, Tokyo 162-8601 (Japan).
authors.forename: Tomoaki
authors.initials: T
authors.lastname: Hashimoto
authors.affiliation: Graduate School of Chemical Sciences and Technology, Tokyo University of Science, 1-3 Kagurazaka, Shinjuku-ku, Tokyo 162-8601 (Japan).
authors.forename: Midori
authors.initials: M
authors.lastname: Yamada
authors.affiliation: Graduate School of Chemical Sciences and Technology, Tokyo University of Science, 1-3 Kagurazaka, Shinjuku-ku, Tokyo 162-8601 (Japan).
authors.forename: Koichiro
authors.initials: K
authors.lastname: Shirai
authors.affiliation: Graduate School of Chemical Sciences and Technology, Tokyo University of Science, 1-3 Kagurazaka, Shinjuku-ku, Tokyo 162-8601 (Japan).
authors.forename: Yuta
authors.initials: Y
authors.lastname: Katagami
authors.affiliation: Graduate School of Chemical Sciences and Technology, Tokyo University of Science, 1-3 Kagurazaka, Shinjuku-ku, Tokyo 162-8601 (Japan).
authors.forename: Tomoaki
authors.initials: T
authors.lastname: Sugaya
authors.affiliation: Graduate School of Chemical Sciences and Technology, Tokyo University of Science, 1-3 Kagurazaka, Shinjuku-ku, Tokyo 162-8601 (Japan). tadokoro@rs.kagu.tus.ac.jp.
authors.forename: Makoto
authors.initials: M
authors.lastname: Tadokoro
authors.affiliation: Graduate School of Chemical Sciences and Technology, Tokyo University of Science, 1-3 Kagurazaka, Shinjuku-ku, Tokyo 162-8601 (Japan). satake@rs.kagu.tus.ac.jp.
authors.forename: Akiharu
authors.initials: A
authors.lastname: Satake
keywords: column chromatography; macrocycles; multinuclear complex; porphyrinoids; synthesis design