Construction and dynamic structural control of hydrindacene-based macrocycles with dimensionally ordered array of functionalities

• Project/Area Number: 20750024
• Research Category: Grant-in-Aid for Young Scientists (B)
• Allocation Type: Single-year Grants
• Research Field: Organic chemistry
• Research Institution: Hokkaido University
• Principal Investigator: KAWAI Hidetoshi Hokkaido University, 大学院・理学研究院, 助教 (50322798)
• Project Period (FY): 2008 – 2009
• Project Status: Completed (Fiscal Year 2009)
• Budget Amount: ¥3,900,000 (Direct Cost: ¥3,000,000、Indirect Cost: ¥900,000); Fiscal Year 2009: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000); Fiscal Year 2008: ¥2,210,000 (Direct Cost: ¥1,700,000、Indirect Cost: ¥510,000)
• Keywords: 構造有機化学 / 化学合成 / マクロサイクル / 動的挙動 / X線構造 / 分子認識 / ナノチューブ / 超分子

Research Abstract

Macrocycles having preorganized, defined cavities and structures of molecular dimensions have attracted great interest due to their novel properties and potential applications. We successfully constructed novel belt-shaped macrocycles with direction-persistent peripheral functionalities in both horizontal and vertical directions to the macrocyclic backbone by using hydrindacene derivatives.

Research Products

• [Journal Article] Drastic change in racemization barrier upon redox reactions: Novel chiral-memory units based on dynamic redox systems (2010)
  • Author(s): T.Suzuki, K.Wada, Y.Ishigaki, Y.Yoshimoto, E.Ohta, H.Kawai, K.Fujiwara
  • Journal Title: Chem.Commun. vol.46(印刷中)
  • Peer Reviewed
• [Journal Article] Drastic change in racemization barrier upon redox reactions : Novel chiral-memory units based on dynamic redox systems (2010)
  • Author(s): T.Suzuki
  • Journal Title: Chemical Communications 46(印刷中)
  • Peer Reviewed
• [Journal Article] Halochromic chiroptical response of novel bis(9-acridinyl)-type fluorophores with a helical π-framework (2010)
  • Author(s): T.Nehira
  • Journal Title: Chemistry Letters 39(3) Pages: 165-167
  • Peer Reviewed
• [Journal Article] Intramolecular triarylmethane-methylium complex : Generation, properties and X-ray structure of C-H bridged carbocation (2010)
  • Author(s): T.Suzuki
  • Journal Title: Pure and Applied Chemistry 82(印刷中)
  • Peer Reviewed
• [Journal Article] Phenanthrene-4,5-diylbis(10-methylacridinium)with a short C^+-C^+ contact : Preparation, molecular structure, redox properties, and electrochromic interconversion with dihydropyrene derivative (2010)
  • Author(s): T.Suzuki
  • Journal Title: Heterocycles 80(1) Pages: 149-155
  • Peer Reviewed
• [Journal Article] Dynamic molecular propeller: Supramolecular chirality sensing by enhanced chiroptical response through the transmission of point chirality to mobile helicity (2009)
  • Author(s): R.Katoono, H.Kawai, K.Fujiwara, T.Suzuki
  • Journal Title: J.Am.Chem.Soc. vol.131,No.46 Pages: 16896-16904
  • Peer Reviewed
• [Journal Article] Multi-input-multi-output molecular response system based on dynamic redox behavior of 3, 3, 4, 4-tetraaryldihydro[5]helicene derivatives: Reversible formation/ destruction of chiral fluorophore and modulation of chiroptical properties by solvent polarity (2009)
  • Author(s): T.Suzuki, Y.Ishigaki, T.Iwai, H.Kawai, K.Fujiwara, H.Ikeda, Y.Kano, K.Mizuno
  • Journal Title: Chem.Eur.J. vol.15,No.37 Pages: 9434-9441
  • Peer Reviewed
• [Journal Article] Negligible diradical character for the ultralong C-C bond in 1, 1, 2, 2- tetraarylpyracene derivatives (2009)
  • Author(s): T.Takeda, H.Kawai, R.Herges, E.Mucke, Y.Sawai, K.Murakoshi, K.Fujiwara, T.Suzuki
  • Journal Title: Tetrahedron Lett. vol.50,No.26 Pages: 3693-3697
  • Peer Reviewed
• [Journal Article] Intramolecular methylacridan-methylacridinium complexes with a phenanthrene-4, 5-diyl or related skeleton: Geometry-properties relationship in isolable C-H bridged carbocations (2009)
  • Author(s): T.Suzuki, Y.Yoshimoto, T.Takeda, H.Kawai, K.Fujiwara
  • Journal Title: Chem.Eur.J. vol.15,No.9 Pages: 2210-2216
  • Peer Reviewed
• [Journal Article] "動的共有結合"で分子の動きを制御する (2009)
  • Author(s): 河合英敏, 梅原健志
  • Journal Title: 現代化学 vol.455,No.2 Pages: 30-35
  • NAID: 40016437096
• [Journal Article] Dynamic molecular propeller : Supramolecular chirality sensing by enhanced chiroptical response through the transmission of point chirality to mobile helicity (2009)
  • Author(s): R.Katoono
  • Journal Title: Journal of the American Chemical Society 131(46) Pages: 16896-16904
  • Peer Reviewed
• [Journal Article] 4, 5-Bis(diarylmethylene)-1, 3-dithiole : A novel helical electron donor exhibiting electrochromic behavior (2009)
  • Author(s): T.Suzuki
  • Journal Title: Chemistry Letters 38(7) Pages: 748-749
  • Peer Reviewed
• [Journal Article] Preparation and X-ray structures of trans-5, 6-diaryl-5, 6-dihydro-1, 10-phenanthroline-5, 6-diols : Formation of supramolecular rod by hydrogen bonds (2009)
  • Author(s): T.Suzuki
  • Journal Title: Chemistry Letters 38(7) Pages: 670-671
  • Peer Reviewed
• [Journal Article] Multi-input-multi-output molecular response system based on dynamic redox behavior of 3, 3, 4, 4-tetraaryldihydro[5]helicene derivatives : Reversible formation/destruction of chiral fluorop hore and modulation of chiroptical properties by solvent polarity (2009)
  • Author(s): T.Suzuki
  • Journal Title: Chemistry-A European Journal 15(37) Pages: 9434-9441
  • Peer Reviewed
• [Journal Article] Negligible diradical character for the ultralong C-C bond in 1, 1, 2, 2-Tetraarylpyracene derivatives (2009)
  • Author(s): T.Takeda
  • Journal Title: Tetrahedron Letters 50(26) Pages: 3693-3697
  • Peer Reviewed
• [Journal Article] "動的共有結合"で分子の動きを制御する (2009)
  • Author(s): 河合英敏
  • Journal Title: 現代化学 455(2) Pages: 30-35
  • NAID: 40016437096
• [Journal Article] Intramolecular methylacridan-methylacridinium complexes with a phenanthrene-4, 5-diyl or related skeleton : Geometry-properties relationship in isolable C-H bridged carbocations (2009)
  • Author(s): T. Suzuki
  • Journal Title: Chemistry-A European Journal 15(9) Pages: 2210-2216
  • Peer Reviewed
• [Journal Article] Entropy- and hydrolytic-driven positional switching of macrocycle between imine- and hydrogen-bonding stations in rotaxane-based molecular shuttles (2008)
  • Author(s): T.Umehara, H.Kawai, K.Fujiwara, T.Suzuki
  • Journal Title: J.Am.Chem.Soc. vol.130,No.42 Pages: 13981-13988
  • Peer Reviewed
• [Journal Article] Designed molecular propellers based on tetraarylterephthalamide and their chiroptical properties induced by biased helicity through transmission of point chirality (2008)
  • Author(s): R.Katoono, H.Kawai, K.Fujiwara, T.Suzuki
  • Journal Title: Chem.Commun. No.40 Pages: 4906-4908
  • NAID: 120001856659
  • Peer Reviewed
• [Journal Article] Ultralong carbon-carbon bonds in dispirobis(10- methylacridan) derivatives with the acenaphthene, pyracene, or dihydropyracylene skeleton (2008)
  • Author(s): H.Kawai, T.Takeda, K.Fujiwara, M.Wakeshima, Y.Hinatsu, T.Suzuki
  • Journal Title: Chem.Eur.J. vol.14,No.19 Pages: 5780-5793
  • Peer Reviewed
• [Journal Article] Entropy- and hydrolytic-driven positional switching of macrocycle between imine-and hydrogen-bonding stations in rotaxane-based molecular shuttles (2008)
  • Author(s): T. Umehara
  • Journal Title: Journal of the American Chemical Society 130(42) Pages: 13981-13988
  • Peer Reviewed
• [Journal Article] Designed molecular propellers based on tetraarylterephthalamide and their chiroptical properties induced by biased helicity through transmission of point chirality (2008)
  • Author(s): R. Katoono
  • Journal Title: Chemical Communications (40) Pages: 4906-4908
  • Peer Reviewed
• [Journal Article] Ultralong carbon-carbon bonds in dispirobis(10-methylacridan) derivatives with an acenaphthene, pyracene, or dihydropyracylene skeleton (2008)
  • Author(s): H. Kawai
  • Journal Title: Chemistry - A European Journal 14(19) Pages: 5780-5793
  • Peer Reviewed
• [Presentation] イミン架橋型ロタキサンユニットを縮重させた[n]ロタキサンの構築とその加水分解挙動 (2010)
  • Author(s): 杉野寛佳
  • Organizer: 日本化学会第90春季年会
  • Place of Presentation: 東大阪
  • Year and Date: 2010-03-28
• [Presentation] アロステリックレセプター誘導体の自己集合に基づく協同的超分子ポリマーの構築と連結鎖の影響 (2010)
  • Author(s): 河合英敏
  • Organizer: 日本化学会第90春季年会
  • Place of Presentation: 東大阪
  • Year and Date: 2010-03-27
• [Presentation] アロステリック会合能が向上したヒドリンダセンヘキサアミドレセプターの構築と会合挙動 (2010)
  • Author(s): 河合英敏
  • Organizer: 日本化学会第90春季年会
  • Place of Presentation: 東大阪
  • Year and Date: 2010-03-27
• [Presentation] イミン結合と水素結合の競争的利用によるロタキサン分子のシャトリング制御 (2010)
  • Author(s): 河合英敏
  • Organizer: 超分子創製化学セミナー(第20回)
  • Place of Presentation: 草津
  • Year and Date: 2010-03-05
• [Presentation] 3次元的な構造修飾性を有するブタジイン架橋ヒドリンダセンマクロサイクルの構築とその物性 (2010)
  • Author(s): 河合英敏
  • Organizer: 化学系学協会北海道支部2010年冬季研究発表会
  • Place of Presentation: 札幌
  • Year and Date: 2010-01-27
• [Presentation] 回転軸を有する光学活性ヒドリンダセン2量体の構築とその機能開発 (2010)
  • Author(s): 河合英敏
  • Organizer: 化学系学協会北海道支部2010年冬季研究発表会
  • Place of Presentation: 札幌
  • Year and Date: 2010-01-27
• [Presentation] アロステリック会合を駆動力とする超分子ポリマー形成 (2009)
  • Author(s): 河合英敏
  • Organizer: 第3回有機π電子系シンポジウム
  • Place of Presentation: 別府
  • Year and Date: 2009-12-05
• [Presentation] アロステリック会合によって駆動される協同的超分子ポリマー形成イミン架橋型螺旋分子における加水分解平衡の調査と外部因子による制御 (2009)
  • Author(s): 河合英敏
  • Organizer: 第20回基礎有機化学討論会
  • Place of Presentation: 桐生
  • Year and Date: 2009-09-29
• [Presentation] イミン架橋型螺旋分子における加水分解平衡の調査と外部因子による制御 (2009)
  • Author(s): 河合英敏
  • Organizer: 第20回基礎有機化学討論会
  • Place of Presentation: 桐生
  • Year and Date: 2009-09-28
• [Presentation] より強いアロステリック会合能を有する新規ヒドリンダセンジアミドレセプターの構築 (2009)
  • Author(s): 河合英敏
  • Organizer: 第20回基礎有機化学討論会
  • Place of Presentation: 桐生
  • Year and Date: 2009-09-28
• [Presentation] Construction of Imine-bridged Helical Structures and Helical Inversion upon Hydrolysis of Imine Bonds (2009)
  • Author(s): 河合英敏
  • Organizer: China-Japan Joint Symposium on Functional Supramolecular Architectures
  • Place of Presentation: Sapporo
  • Year and Date: 2009-08-04
• [Presentation] Rotaxane Synthesis via Imine-bridged Rotaxane and Their Dynamic Equilibrium : Structural Effects of Imine-bridging Station and Macrocycle (2009)
  • Author(s): 河合英敏
  • Organizer: China-Japan Joint Symposium on Functional Supramolecular Architectures
  • Place of Presentation: Sapporo
  • Year and Date: 2009-08-04
• [Presentation] Allosteric Binding-Driven Cooperative Supramolecular Polymerization (2009)
  • Author(s): 河合英敏
  • Organizer: China-Japan Joint Symposium on Functional Supramolecular Architectures
  • Place of Presentation: Sapporo
  • Year and Date: 2009-08-04
• [Presentation] Construction of Imine-bridged Rotaxanes and Their Dynamic Equilibrium: Structural Effects of Imine-bridging Station and Macrocycle (2009)
  • Author(s): H.Kawai
  • Organizer: The IV joint International Symposium on Macrocyclic & Supramolecular Chemistry (ISMSC-2009)
  • Place of Presentation: Maastricht
  • Year and Date: 2009-06-22
• [Presentation] Construction of Imine-bridged Rotaxanes and Their Dynamic Equilibrium : Structural Effects of Imine-bridging Station and Macrocycle (2009)
  • Author(s): 河合英敏
  • Organizer: The IV joint International Symposium on Macrocyclic & Supramolecular Chemistry(ISMSC-2009)
  • Place of Presentation: Maastricht, Nederland
  • Year and Date: 2009-06-22
• [Presentation] Cooperative Supramolecular Polymers using Positive Allosteric Receptors (2009)
  • Author(s): 河合英敏
  • Organizer: The IV joint International Symposium on Macrocyclic & Supramolecular Chemistry(ISMSC-2009)
  • Place of Presentation: Maastricht, Nederland
  • Year and Date: 2009-06-22
• [Presentation] イミン架橋による螺旋構造の反転制御 (2009)
  • Author(s): 河合英敏
  • Organizer: 日本化学会第89春季年会
  • Place of Presentation: 舟橋
  • Year and Date: 2009-03-30
• [Presentation] Imine-bridged Rotaxanes : Structural Effects toward Imine-directed Threading and Hydrolytic Equilibrium (2009)
  • Author(s): Hidetoshi Kawai
  • Organizer: International Symposium for Environmental Inno vatibn Driven by Chemistry and Catalytic Science
  • Place of Presentation: Sapporo
  • Year and Date: 2009-03-18
• [Presentation] 核形成一伸長プロセスに基づく超分子ポリマー化を目指したアロステリックモノマー分子の構築 : レセプター-ゲスト間のリンカー長の影響 (2009)
  • Author(s): 河合英敏
  • Organizer: 化学系学協会北海道支部2009年冬季研究発表会
  • Place of Presentation: 札幌
  • Year and Date: 2009-02-04
• [Presentation] ヒドリンダセンジアミドレセプターの構造修飾によるアロステリック会合強度向上の検討 (2009)
  • Author(s): 河合英敏
  • Organizer: 化学系学協会北海道支部2009年冬季研究発表会
  • Place of Presentation: 札幌
  • Year and Date: 2009-02-04
• [Presentation] 種々の軸分子を用いたイミン架橋型ロタキサンの構築とその加水分解挙動 (2009)
  • Author(s): 河合英敏
  • Organizer: 化学系学協会北海道支部2009年冬季研究発表会
  • Place of Presentation: 札幌
  • Year and Date: 2009-02-04
• [Presentation] イミン結合ステーションと水素結合ステーション問でマクロサイクルの位置がエントロピー的に制御されるロタキサン分子シャトル (2008)
  • Author(s): 河合英敏
  • Organizer: 第2回福岡万有若手合宿セミナー
  • Place of Presentation: 上天草
  • Year and Date: 2008-11-15
• [Presentation] Structural Effects of an Imine-bridging Station on Construction of Imine-bridged Rotaxanes and Their Dynamic Eauilibrium upon hydrolysis of the Imine Bonds (2008)
  • Author(s): Hidetoshi Kawai
  • Organizer: Japan-Korea-China Mini-symposium on Nanotechnology, Biotechnology and Catalysis
  • Place of Presentation: Sapporo
  • Year and Date: 2008-11-07
• [Presentation] イミン架橋型らせん構造の構築と加水分解による螺旋反転挙動の調査 (2008)
  • Author(s): 河合英敏
  • Organizer: 第19回基礎有機化学討論会
  • Place of Presentation: 吹田
  • Year and Date: 2008-10-04
• [Presentation] イミン架橋型ロタキサンの構築と加水分解平衡に与えるイミン架橋ステーシヨンの構造的影響 (2008)
  • Author(s): 河合英敏
  • Organizer: 第19回基礎有機化学討論会
  • Place of Presentation: 吹田
  • Year and Date: 2008-10-04
• [Presentation] ヒドリンダセン-2, 6-ジカルボニトリル誘導体を双極回転子として有するマクロサイクルの構築とその回転配向制御 (2008)
  • Author(s): 河合英敏
  • Organizer: 第19回基礎有機化学討論会
  • Place of Presentation: 大阪
  • Year and Date: 2008-10-03
• [Presentation] ヒドリンダセン-2,6-ジカルボニトリル誘導体を双極回転子として有するマクロサイクルの構築とその回転配向制御 (2008)
  • Author(s): 河合英敏
  • Organizer: 第19回基礎有機化学討論会
  • Place of Presentation: 吹田
  • Year and Date: 2008-10-03
• [Presentation] Entropy- and Hydrolytic-Driven Positional Switching of Macrocycle between Imine- and Hydrogen-Bonding Stations in Rotaxane-Based Molecular Shuttles (2008)
  • Author(s): 河合英敏
  • Organizer: Yamada Conference: Topological Molecules
  • Place of Presentation: Awaji
  • Year and Date: 2008-09-03
• [Presentation] Entropy-and Hydrolytic-Driven Positional Switching of Macrocycle between Imine-and Hydrogen-Bonding Stations in Rotaxane-Based Molecular Shuttles (2008)
  • Author(s): Hidetoshi Kawai
  • Organizer: Yamada Conference : Topological Molecules
  • Place of Presentation: Awaji
  • Year and Date: 2008-09-03
• [Presentation] ロタキサン分子シャトルにおけるエントロピー駆動スイッチング:イミン結合と水素結合の競争的利用 (2008)
  • Author(s): 河合英敏
  • Organizer: 第3回ホスト・ゲストシンポジウム
  • Place of Presentation: 東京
  • Year and Date: 2008-05-31
• [Presentation] イミン架橋された螺旋構造の構築とその加水分解に伴う螺旋反転 (2008)
  • Author(s): 河合英敏
  • Organizer: 第3回ホスト・ゲストシンポジウム
  • Place of Presentation: 東京
  • Year and Date: 2008-05-31
• [Presentation] ロタキサン分子シャトルにおけるエントロピー駆動スイッチング : イミン結合と水素結合の競争的利用 (2008)
  • Author(s): 河合英敏
  • Organizer: 第3回ホスト・ゲストシンポジウム
  • Place of Presentation: 東京
  • Year and Date: 2008-05-31
• [Book] Strained Hydrocarbons: Beyond the van't Hoff and Le Bel Hypothesis(H.Dodziuk, Ed.) (2009)
  • Author(s): T.Suzuki, T.Takeda, H.Kawai, K.Fujiwara, (H.Dodziuk, Ed.)
  • Publisher: WILEY-VCH
• [Book] Strained Hydrocarbons : Beyond the van't Hoff and Le Bel Hypothesis (2009)
  • Author(s): T. Suzuki (H. Dodziuk, Ed.)
  • Total Pages: 492
  • Publisher: Wiley-VCH