Synthesis and Response toward External Stimulli of Bithiophene Derivatives Bridged by Spirodienone Structure

• Project/Area Number: 20550039
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Organic chemistry
• Research Institution: Osaka University
• Principal Investigator: KURATA Hiroyuki Osaka University, 理学研究科, 講師 (40263199)
• Project Period (FY): 2008 – 2010
• Project Status: Completed (Fiscal Year 2010)
• Budget Amount: ¥4,290,000 (Direct Cost: ¥3,300,000、Indirect Cost: ¥990,000); Fiscal Year 2010: ¥780,000 (Direct Cost: ¥600,000、Indirect Cost: ¥180,000); Fiscal Year 2009: ¥1,170,000 (Direct Cost: ¥900,000、Indirect Cost: ¥270,000); Fiscal Year 2008: ¥2,340,000 (Direct Cost: ¥1,800,000、Indirect Cost: ¥540,000)
• Keywords: チオフェン / 分子スイッチング / 酸化還元系 / メカノクロミズム / スピロ構造 / アモルファス / ビラジカル / 粉末X線回折 / ジスピロ構造 / 合成化学 / 分子機械 / 分子スイッチ / サイクリックボルタンメトリー

Research Abstract

Bithiophene derivtives bridged with a bis (spirodienone) unit were synthesized and characterized. Palladium-catalyzed cross-coupling reactions with bromides afforded a variety of pi-extended derivatives. In these compounds, bond breaking and formation under redox conditions were observed by cyclic voltammetry (CV). Especially, 2,2'-bridged-3,3'-bithiophene derivatives showed significant temperature- and scan rate-dependence on CV. These phenomena indicate the existence of the equilibrium between dispiro-compounds and open-ring biradicals. Furthermore, mechanochromism, N,N-dialkylaminophenyl-substituted 2,2'-bridged-3,3'-bithiophene derivatives showed mechanochromism. During grinding the crystals, the color was changed from yellow to reddish orange, and by exposure to organic solvents, the reddish-orange color was immediately turned back to yellow.

Research Products

• [Journal Article] An effective Synthesis of N,N-Dimethyl- amides from Carboxylic Acids and a New Route from N,N-Dimethylamides to 1,2- Diaryl-1,2-diketones. (2010)
  • Author(s): T.Kumagai, T.Anki, T.Ebi, A.Konishi, K.Matsumoto, H.Kurata, T.Kubo, K.Katsumoto, C.Kitamura T.Kawase
  • Journal Title: Tetrahedron 66(46) Pages: 8968-8973
  • Peer Reviewed
• [Journal Article] Dinaphthopentalenes : Pentalene Derivatives for Organic Thin-Film Transistors. (2010)
  • Author(s): T.Kawase, T.Fujiwara, C.Kitamura, A.Konishi, Y.Hirao, K.Matsumoto, H.Kurata, T.Kubo, S.Shinamura, H.Mori, E.Miyazaki, K.Takimiya
  • Journal Title: Angewandte Chemie International Edition 49(42) Pages: 7728-7732
  • Peer Reviewed
• [Journal Article] Alternating Covalent Bonding Inter- actions in a One-Dimensional Chain of a Phenalenyl- Based Singlet Biradical Molecule Having Kekule Structures. (2010)
  • Author(s): A.Shimizu, T.Kubo, M.Uruichi, K.Yakushi, M.Nakano, D.Shiomi, K.Sato, T.Takui, Y.Hirao, K.Matsumoto, H.Kurata, Y.Morita, K.Nakasuji
  • Journal Title: Journal of the American Chemical Society 132(41) Pages: 14421-14428
  • Peer Reviewed
• [Journal Article] Synthesis and Characterization of Teranthene : A Singlet Biradical Polycyclic Aromatic Hydrocarbon Having Kekule Structures. (2010)
  • Author(s): A.Konishi, Y.Hirao, M.Nakano, A.Shimizu, E.Botek, B.Champagne, D.Shiomi, K.Sato, T.Takui, K.Matsumoto, H.Kurata, T.Kubo
  • Journal Title: Journal of the American Chemical Society 132(32) Pages: 11021-11023
  • Peer Reviewed
• [Journal Article] Hydrogen-Bonded Quartz-type Network of Diprotonated Tetrakis(4-pyridyl)- methane Dications. (2010)
  • Author(s): K.Matsumoto, D.Inokuchi, Y.Hirao, H.Kurata, T.Kubo
  • Journal Title: Crystal Growth & Design 10(7) Pages: 2854-2856
  • Peer Reviewed
• [Journal Article] Synthesis and Identification of a Trimethylenemethane Derivative π-Extended with Three Pyridinyl Radicals. (2010)
  • Author(s): K.Matsumoto, D.Inokuchi, Y.Hirao, H.Kurata, K.Sato, T.Takui, T.Kubo
  • Journal Title: Organic Letters 12(4) Pages: 836-839
  • Peer Reviewed
• [Journal Article] Pentaleno[1,2-c:4,5-c']dithiophene Derivatives : First Synthesis, Properties, and a Molecular Structure. (2010)
  • Author(s): A.Konishi, T.Fujiwara, N.Ogawa, Y.Hirao, K.Matsumoto, H.Kurata, T.Kubo, C.Kitamura, T.Kawase
  • Journal Title: Chemistry Letters 39(3) Pages: 300-301
  • NAID: 10027178748
  • Peer Reviewed
• [Journal Article] An effective synthesis of N,N-dimethylamides from carboxylic acids and a new route from N,N-dimethylamides to 1,2-diaryl-1,2-diketones (2010)
  • Author(s): Takashi Kumagai, Hiroyuki Kurata
  • Journal Title: Tetrahedron Volume: 66 Pages: 8968-8973
  • Peer Reviewed
• [Journal Article] Dinaphthopentalenes : Pentalene Derivatives for Organic Thin-Film Transistors (2010)
  • Author(s): Takeshi Kawase, Hiroyuki Kurata
  • Journal Title: Angewandte Chemie, International Edition Volume: 49 Pages: 7728-7732
  • Peer Reviewed
• [Journal Article] Alternating Covalent Bonding Interactions in a One-Dimensional Chain of a Phenalenyl-Based Singlet Biradical Molecule Having Kekule Structures (2010)
  • Author(s): Akihiro Shimizu, Hiroyuki Kurata
  • Journal Title: Journal of the American Chemical Society Volume: 132 Pages: 14421-14428
  • Peer Reviewed
• [Journal Article] Synthesis and Characterization of Teranthene : A Singlet Biradical Polycyclic Aromatic Hydrocarbon Having Kekule Structures (2010)
  • Author(s): Akihito Konishi, Hiroyuki Kurata
  • Journal Title: Journal of the American Chemical Society Volume: 132 Pages: 11021-11023
  • Peer Reviewed
• [Journal Article] Hydrogen-Bonded Quartz-type Network of Diprotonated Tetrakis(4-pyridyl)methane Dications (2010)
  • Author(s): Kouzou Matsumoto, Hiroyuki Kurata
  • Journal Title: Crystal Growth & Design Volume: 10 Pages: 2854-2856
  • Peer Reviewed
• [Journal Article] Synthesis and Identification of a Trimethylenemethane Derivative π-Extended with Three Pyridinyl Radicals (2010)
  • Author(s): Kouzou Matsumoto, Hiroyuki Kurata
  • Journal Title: Organic Letters Volume: 12 Pages: 836-839
  • Peer Reviewed
• [Journal Article] Pentaleno[1,2-c : 4,5-c']dithiophene Derivatives : First Synthesis, Properties, and a Molecular Structure (2010)
  • Author(s): Akihito Konishi
  • Journal Title: Chemistry Letters 39 Pages: 300-301
  • Peer Reviewed
• [Journal Article] Resonance Balance Shift in π-π One-Dimensional Chain of Delocalized Singlet Biradical. (2009)
  • Author(s): A.Shimizu, M.Uruichi, K.Yakushi, H.Matsuzaki, H.Okamoto, M.Nakano, Y.Hirao, K.Matsumoto, H.Kurata, T.Kubo
  • Journal Title: Angewandte Chemie, International Edition 48(30) Pages: 5482-5486
  • Peer Reviewed
• [Journal Article] Shape-Persistent, Double-Helically Twisted Macrocycles with Two Quaterphenyl Moieties : Synthesis, Structure and Physicochemical Properties for a Chiral Sensor. (2009)
  • Author(s): T.Kawase, Y.Daifuku, Y.Hirao, K.Matsumoto, H.Kurata, T.Kubo
  • Journal Title: Comptes Rendus Chimie 12(3-4) Pages: 403-411
  • Peer Reviewed
• [Journal Article] An Extremely Simple Dibenzopentalene Synthesis from 2-Bromo-1-ethynyl- benzenes Using Nickel(0) Complexes : Construction of Its Derivatives with Various Functionalities. (2009)
  • Author(s): T.Kawase, A.Konishi, Y.Hirao, K.Matsumoto, H.Kurata, T.Kubo
  • Journal Title: Chemistry- A European Journal 15(11) Pages: 2653-2661
  • Peer Reviewed
• [Journal Article] Resonance Balance Shift in π-π One-Dimensional Chain of Delocalized Singlet Biradical (2009)
  • Author(s): Akihiro Shimizu
  • Journal Title: Angewandte Chemie, International Edition 48 Pages: 5482-5486
  • Peer Reviewed
• [Journal Article] Shape-Persistent, Double-Helically Twisted Macrocycles with Two Quaterphenyl Moieties : Synthesis, Structure and Physicochemical Properties for a Chiral Sensor (2009)
  • Author(s): Takeshi Kawase
  • Journal Title: Comptes Rendus Chimie 12 Pages: 403-411
  • Peer Reviewed
• [Journal Article] Shape-Persistent, Double-Helically Twisted Macrocycles with TwoQuaterphenyl Moieties : Synthesis, Structure and PhysicochemicalProperties for a Chiral Sensor (2009)
  • Author(s): 川瀬 毅
  • Journal Title: Comptes Rendus Chimie 12 Pages: 403-411
  • Peer Reviewed
• [Journal Article] An Extremely Simple Dibenzopentalene Synthesis from2-Bromo-1-ethynylbenzenes Using Nickel(O)Complexes : Construction ofIts Derivatives with Various Functionalities (2009)
  • Author(s): 川瀬 毅
  • Journal Title: Chemistry-A European Journal 15 Pages: 2653-2661
  • Peer Reviewed
• [Journal Article] Chiral Tetrakis(2-thienyl)methane Derivative : A Possible Precursor for Cryptochiral Tetraalkylmethanes. (2008)
  • Author(s): K.Matsumoto, K.Miki, H.Kurata, N.Rikitake, T.Nehira, T.Inagaki, G.Pescitelli, Y.Hirao, T.Kawase, M.Oda, T.Kubo
  • Journal Title: Chemistry Letters 37(12) Pages: 1236-1237
  • NAID: 10024397925
  • Peer Reviewed
• [Journal Article] Tetrahedral Oligothiophenes ; Synthesis, X-ray Analysis, and Optoelectronic Properties of Highly Symmetrical, 3D-Branched Oligothiophenes. (2008)
  • Author(s): K.Matsumoto, T.Tanaka, S.Kugo, T.Inagaki, Y.Hirao, H.Kurata, T.Kawase, T.Kubo
  • Journal Title: Chemistry- An Asian Journal 3(12) Pages: 2024-2032
  • Peer Reviewed
• [Journal Article] The First Synthesis of 2,2':5',2"- Terthiazole. (2008)
  • Author(s): H.Kurata, H.Takakuwa, K.Matsumoto, T.Kawase, M.Oda
  • Journal Title: Synlett 18 Pages: 2882-2884
  • Peer Reviewed
• [Journal Article] Synthesis and Functionalization of 3,3-Bis(spirodienone)-Bridged 2,2-Bithiophene : A New Building Block for Redox-Active Molecular Switching Materials. (2008)
  • Author(s): H.Kurata, S.Kim, T.Fujimoto, K.Matsumoto, T.Kawase, T.Kubo
  • Journal Title: Organic Letters 10(17) Pages: 3837-3840
  • Peer Reviewed
• [Journal Article] 8,14,30,36-Tetramethoxy[2.0.2.0](1,6) naphthalenophane-1,19-diyne : A Double-Helically Twisted Cyclophane by Diastereoselective Dimerization. (2008)
  • Author(s): T.Kawase, T.Nakamura, K.Utsumi, K.Matsumoto, H.Kurata, M.Oda
  • Journal Title: Chemistry- An Asian Journal 3(3) Pages: 573-577
  • Peer Reviewed
• [Journal Article] Chiral Tetrakis(2-thienyl)methane Derivative : A Possible Precursor forCryptochiral Tetraalkylmethanes (2008)
  • Author(s): 松本幸三
  • Journal Title: Chemistry Letters 37 Pages: 1236-1237
  • Peer Reviewed
• [Journal Article] Tetrahedral oligothiophenes ; synthesis, X-ray analysis, and optoelectronicproperties of highly symmetrical. 3D-branched oligothiopheaes (2008)
  • Author(s): 松本幸三
  • Journal Title: Chemistry-An Asian Journal 3 Pages: 2024-2032
  • Peer Reviewed
• [Journal Article] The First Synthesis of 2, 2' : 5', 2"-Terthiazole (2008)
  • Author(s): 蔵田浩之
  • Journal Title: Synlett Pages: 2882-2884
  • Peer Reviewed
• [Journal Article] Synthesis and Functionalization of 3, 3-Bis(spirodienone)-Bridged2, 2-Bithiophene : A New Building Block for Redox-Active MolecularSwitching Materials (2008)
  • Author(s): 蔵田浩之
  • Journal Title: Organic Letters 10 Pages: 3837-3840
  • Peer Reviewed
• [Presentation] Synthesis and Properties of 2,2'-Bis(spirodienone)-Bridged-3,3'-Bithiophene Derivatives-An Unusual Redox Behavior Coused by Ring-Opening (2010)
  • Author(s): 蔵田浩之
  • Organizer: The International Chemical Congress of Pacific Basin Societies (Pacifichem 2010)
  • Place of Presentation: Honolulu, Hawaii (USA)
  • Year and Date: 2010-12-17
• [Presentation] Mechanochromism of 2, 2'-Bis(spirodienone)-Bridged-3, 3'-Bithiophene Derivatives (2010)
  • Author(s): 蔵田浩之
  • Organizer: The International Chemical Congress of Pacific Basin Societies (Pacifichem 2010)
  • Place of Presentation: Honolulu, Hawaii (USA)
  • Year and Date: 2010-12-17
• [Presentation] 2,2'-ビス(スピロジエノン)-3,3'-ビチオフェン誘導体のメカノクロミズム (2010)
  • Author(s): 蔵田浩之
  • Organizer: 第21回基礎有機化学討論会
  • Place of Presentation: 名古屋大学(名古屋市)
  • Year and Date: 2010-09-10
• [Presentation] ビラジカル性を有する拡張キノン系分子の合成と性質 (2010)
  • Author(s): 蔵田浩之
  • Organizer: シンポジウム「電子状態理論の新機軸」
  • Place of Presentation: 岡崎コンファレンスセンター(岡崎市)
  • Year and Date: 2010-08-10
• [Presentation] 2, 2'-ビス (スピロジエノン) 架橋-3, 3'-ビチオフェン誘導体のメカノクロミズム (2010)
  • Author(s): 蔵田浩之
  • Organizer: 日本化学会第90春季年会
  • Place of Presentation: 東大阪 (近畿大学)
  • Year and Date: 2010-03-29
• [Presentation] Synthesis and Properties of 2,2'-Bis(spirodienone)-Bridged-3,3'- Bithiophene Derivatives -An Unusual Redox Behavior Coused by Ring- Opening. (2010)
  • Author(s): 蔵田浩之, 藤本貴久, 阿辻裕美子, 平尾泰一, 松本幸三, 久保孝史
  • Organizer: The International Chemical Congress of Pacific Basin Societies (Pacifichem 2010)
  • Place of Presentation: Honolulu, Hawaii, USA
• [Presentation] Mechanochromism of 2,2'-Bis(spiro- dienone)-Bridged-3,3'-Bithiophene Derivatives. (2010)
  • Author(s): 蔵田浩之, 阿辻裕美子, 平尾泰一, 松本幸三, 網本貴一, 久保孝史
  • Organizer: The International Chemical Congress of Pacific Basin Societies (Pacifichem 2010)
  • Place of Presentation: Honolulu, Hawaii, USA
• [Presentation] 2,2'-ビス(スピロジエノン)-3,3'-ビチオフェン誘導体のメカノクロミズム (2010)
  • Author(s): 蔵田浩之・阿辻裕美子・平尾泰一・松本幸三・網本貴一・久保孝史
  • Organizer: 第21回基礎有機化学討論会
  • Place of Presentation: 名古屋(名古屋大学)
• [Presentation] ビラジカル性を有する拡張キノン系分子の合成と性質 (2010)
  • Author(s): 蔵田浩之・阿辻裕美子・小西彬仁・平尾泰一・松本幸三・久保孝史
  • Organizer: シンポジウム「電子状態理論の新機軸」
  • Place of Presentation: 岡崎(岡崎コンファレンスセンター)
• [Presentation] 2,2'-ビス(スピロジエノン)架橋-3,3'-ビチオフェン誘導体のメカノクロミズム (2010)
  • Author(s): 阿辻裕美子・蔵田浩之・藤本貴久・平尾泰一・松本幸三・網本貴一・久保孝史
  • Organizer: 日本化学会第90春季年会
  • Place of Presentation: 東大阪(近畿大学)
• [Presentation] ビス(スピロジエノン)架橋ビチオフェン類の合成と特異な酸化還元挙動 (2008)
  • Author(s): 藤本貴久・蔵田浩之・平尾泰一・松本幸三・久保孝史
  • Organizer: 第35回有機典型元素化学討論会
  • Place of Presentation: 八王子(首都大東京)
• [Presentation] ビス(スピロジエノン)構造で架橋されたビチオフェン誘導体の合成・構造・反応性 (2008)
  • Author(s): 蔵田浩之・藤本貴久・金 翔・平尾泰一・松本幸三・川瀬毅・久保孝史
  • Organizer: 第19回基礎有機化学討論会
  • Place of Presentation: 吹田(大阪大学)
• [Presentation] ビス(スピロジェノン)架橋ビチオフェン類の合成と特異な酸化還元挙動 (2008)
  • Author(s): 藤本貴久
  • Organizer: 第35回有機典型元素化学討論会
  • Place of Presentation: 八王子(首都大東京)
• [Presentation] 2, 2'-ビス(スピロジェノン)架橋3, 3'-ビチオフェン類の合成とその特異な酸化還元挙動 (2008)
  • Author(s): 藤本貴久
  • Organizer: 第19回基礎有機化学討論会
  • Place of Presentation: 吹田(大阪大学)
• [Remarks]
  • URL: http://www.chem.sci.osaka-u.ac.jp/lab/kubo/Start.html