Synthesis of Three-Dimensionally Extended Giant Oligothiophenes Based on Tetrathienylmethane

• Project/Area Number: 21750045
• Research Category: Grant-in-Aid for Young Scientists (B)
• Allocation Type: Single-year Grants
• Research Field: Organic chemistry
• Research Institution: Osaka University
• Principal Investigator: MATSUMOTO Kouzou Osaka University, 大学院・理学研究科, 助教 (40311766)
• Project Period (FY): 2009 – 2010
• Project Status: Completed (Fiscal Year 2010)
• Budget Amount: ¥4,680,000 (Direct Cost: ¥3,600,000、Indirect Cost: ¥1,080,000); Fiscal Year 2010: ¥1,560,000 (Direct Cost: ¥1,200,000、Indirect Cost: ¥360,000); Fiscal Year 2009: ¥3,120,000 (Direct Cost: ¥2,400,000、Indirect Cost: ¥720,000)
• Keywords: 機能性有機材料 / オリゴチオフェン / デンドリマー / 構造有機化学 / X線結晶構造解析 / 示差走査熱量測定 / 機能性有機分子 / 合成有機化学 / 拡張π電子系化合物 / 材料科学

Research Abstract

A series of the derivatives of tetrakis(2-thienyl)methane extended with further thiophene rings have been synthesized. These derivatives exhibited the longer absorption and fluorescence wavelengths than those of the corresponding linear analogues. It should be noted that these derivatives not only showed the high tendency to crystallize reflecting the highly symmetric molecular structure but also the stable amorphous state based on the many stable conformers.

Research Products

• [Journal Article] Marking the nitrogen atoms of phenyl-(2-pyridyl)-(3-pyridyl)-(4-pyridyl)methane. (2011)
  • Author(s): K.Matsumoto, K.Miki, T.Inagaki, T.Nehira, G.Pescitelli, Y.Hirao, H.Kurata, T.Kawase, T.Kubo
  • Journal Title: Synthesis and absolute configuration of the corresponding tris(pyridine N-oxide) Chirality 23巻(ページ未定)
  • Peer Reviewed
• [Journal Article] "Marking" the nitrogen atoms of phenyl-(2-pyridyl)-(3-pyridyl)-(4-pyridyl)-methane.Synthesis and absolute configuration of the corresponding tris(pyridine N-oxide) (2011)
  • Author(s): 松本幸三
  • Journal Title: Chirality Volume: 23(掲載確定)
  • 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: Angew.Chem.Int.Ed. 49巻 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): 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: J.Am.Chem.Soc. 132巻 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: J.Am.Chem.Soc. 132巻 Pages: 11021-11023
  • 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): T.Kumagai, T.Anki, T.Ebi, A.Konishi,K.Matsumoto, H.Kurata, T.Kubo, K.Katsumoto, C.Kitamura, T.Kawase
  • Journal Title: Tetrahedron 66巻 Pages: 8968-8973
  • 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: Cryst.Growth Des. 10巻 Pages: 2854-2856
  • 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: Chem.Lett. 39巻 Pages: 300-301
  • NAID: 10027178748
  • 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: Org.Lett. 12巻 Pages: 836-839
  • Peer Reviewed
• [Journal Article] Hydrogen-Bonded Quartz-type Network of Diprotonated Tetrakis-(4-pyridyl)methane Dications (2010)
  • Author(s): 松本幸三
  • Journal Title: Crystal Growth & Design Volume: 10 Pages: 2854-2856
  • Peer Reviewed
• [Journal Article] Synthesis and Characterization of Teranthene : A Singlet Biradical Polycylic Aromatic Hydrocarbon Having Kekule Structures (2010)
  • Author(s): 小西彬仁、松本幸三
  • Journal Title: Journal of the American Chemical Society Volume: 132 Pages: 11021-11023
  • 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): 清水章弘、松本幸三
  • Journal Title: Journal of the American Chemical Society Volume: 132 Pages: 14421-14428
  • Peer Reviewed
• [Journal Article] Synthesis and Identification of a Trimethylenemethane Derivative π-Extended with Three Pyridinyl Radicals (2010)
  • Author(s): Kouzou Matsumoto
  • Journal Title: Organic Letters 12 Pages: 836-839
  • Peer Reviewed
• [Journal Article] Magnetic Properties of Iron(II) and Cobalt(II) Complexes of Tetrakis(2-pyridyl)methane (2009)
  • Author(s): R.Ishikawa, K.Matsumoto, K.Onishi, T.Kubo, A.Fuyuhiro, S.Hayami, K.Inoue, S.Kaizaki, S.Kawata
  • Journal Title: Chem.Lett. 38巻 Pages: 620-621
  • Peer Reviewed
• [Journal Article] Resonance Balance Shift in Stacks of Delocalized Singlet Biradicals (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: Angew.Chem.,Int.Ed. 48巻 Pages: 5482-5486
  • Peer Reviewed
• [Journal Article] Magnetic Properties of Iron(II) and Cobalt(II) Complexes of Tetrakis(2-pyridyl)methane. Spin-crossover Behavior in the Cobalt(II) Complex (2009)
  • Author(s): Ryuta Ishikawa
  • Journal Title: Chemistry Letters 38 Pages: 620-621
  • Peer Reviewed
• [Journal Article] Resonance Balance Shift in Stacks of Delocalized Singlet Biradicals (2009)
  • Author(s): Akihiro Shimizu
  • Journal Title: Angewandte Chemie International Edition 48 Pages: 5482-5486
  • Peer Reviewed
• [Presentation] テトラキス(4-ピリジル)メタンジプロトン付加体が作る水晶型ネットワークの構造と物性 (2011)
  • Author(s): 猪口大輔・平尾泰一・高橋一志・松本幸三・蔵田浩之・森初果・久保孝史
  • Organizer: 日本化学会第91春季年会
  • Place of Presentation: 神奈川大学
  • Year and Date: 2011-03-28
• [Presentation] Studies on the synthesis and properties of dendrimer molecule based on tetrakis(2-thienyl)-methane framework (2010)
  • Author(s): S.Kugo, K.Matsumoto, D.Takajo, Y.Hirao, H.Kurata, T.Kubo
  • Organizer: 2010 International Chemical Congress of Pacific Basin Societies (PACIFICHEM 2010)
  • Place of Presentation: ホノルル,アメリカ
  • Year and Date: 2010-12-17
• [Presentation] Synthesis of the novel ligands based on tetrakis(2-pyridyl)- methane and their metal complexes (2010)
  • Author(s): K.Kawashita, K.Matsumoto, Y.Hirao, H.Kurata, T.Kubo
  • Organizer: 2010 International Chemical Congress of Pacific Basin Societies (PACIFICHEM 2010)
  • Place of Presentation: ホノルル,アメリカ
  • Year and Date: 2010-12-17
• [Presentation] Studies on the synthesis and properties of dendrimer molecule based on tetrakis(2-thienyl)methane framework (2010)
  • Author(s): 久後聡太、松本幸三
  • Organizer: 2010 International Chemical Congress of Pacific Basin Societies (PACIFICHEM 2010)
  • Place of Presentation: Honolulu, USA
  • Year and Date: 2010-12-17
• [Presentation] アゾ化合物を経由したテトラキス(4-ピリジル)メタンの改良合成法の開発とその反応機構の解明 (2010)
  • Author(s): 猪口大輔、松本幸三
  • Organizer: 第4回有機π電子系シンポジウム
  • Place of Presentation: 神戸シーパル須磨
  • Year and Date: 2010-11-19
• [Presentation] 4-アミノピリジン-3-チオールを配位子とする金属錯体の合成研究 (2010)
  • Author(s): 北山直樹、松本幸三
  • Organizer: 第4回有機π電子系シンポジウム
  • Place of Presentation: 神戸シーパル須磨
  • Year and Date: 2010-11-19
• [Presentation] sp3炭素原子に四つのπラジカルを導入したテトララジカルの合成検討 (2010)
  • Author(s): 小林憲二、松本幸三
  • Organizer: 第4回有機π電子系シンポジウム
  • Place of Presentation: 神戸シーパル須磨
  • Year and Date: 2010-11-19
• [Presentation] テトラキス(4-ピリジル)メタンを架橋配位子に用いた金属錯体の結晶構造と磁気的性質 (2010)
  • Author(s): 猪口大輔・松本幸三・平尾泰一・蔵田浩之・久保孝史
  • Organizer: 第4回分子科学討論会
  • Place of Presentation: 大阪大学
  • Year and Date: 2010-09-15
• [Presentation] Straightforward Synthesis of Tetraarylmethane Derivatives from the Corresponding Triarylmethyl Anion (2010)
  • Author(s): K.Matsumoto, S.Kugo, K.Miki, R.Tanaka, K.Kawashita, D.Inokuchi, Y.Hirao, H.Kurata, T.Kubo
  • Organizer: 9th International Symposium on Carbanion Chemistry (ISCC-9)
  • Place of Presentation: フィレンツェ大学,イタリア
  • Year and Date: 2010-07-23
• [Presentation] Straightforward Synthesis of Tetraarylmethane Derivatives from the Corresponding Triarylmethyl Anion (2010)
  • Author(s): 松本幸三
  • Organizer: 9th International Symposium on Carbanion Chemistry (ISCC-9)
  • Place of Presentation: Florence, Italy
  • Year and Date: 2010-07-23
• [Presentation] Crystal Structures and Properties of the Salts of Diprotonated Tetrakis(4-pyridyl)methane (2010)
  • Author(s): D.Inokuchi, K.Matsumoto, Y.Hirao, H.Kurata, T.Kubo
  • Organizer: International Conference on Science and Technology of Synthetic Metals (ICSM 2010)
  • Place of Presentation: 京都国際会館
  • Year and Date: 2010-07-06
• [Presentation] Crystal Structure and Properties of the Salts of Diprotonated Tetrakis(4-pyridyl)methane (2010)
  • Author(s): 猪口大輔、松本幸三
  • Organizer: International Conference on Science and Technology of Synthetic Metals 2010 (ICSM 2010)
  • Place of Presentation: 京都国際会館
  • Year and Date: 2010-07-06
• [Presentation] テトラキス(2-チエニル)メタンを基盤とするデンドリマー分子の合成研究 (2010)
  • Author(s): 久後聡太・松本幸三・平尾泰一・蔵田浩之・久保孝史
  • Organizer: 日本化学会第90春季年会
  • Place of Presentation: 近畿大学
  • Year and Date: 2010-03-26
• [Presentation] テトラキス(2-チエニル)メタンを基盤とするデンドリマー分子の合成研究 (2010)
  • Author(s): 久後聡太
  • Organizer: 日本化学会第90春季年会
  • Place of Presentation: 近畿大学(大阪)
• [Presentation] プロトン共役電子移動を指向した4-アミノピリジン-3-チオールを配位子とする金属錯体の合成研究 (2010)
  • Author(s): 北山直樹
  • Organizer: 日本化学会第90春季年会
  • Place of Presentation: 近畿大学(大阪)
• [Presentation] テトラキス(4-ピリジル)メタンの改良合成法とそのプロトン化体の結晶構造 (2010)
  • Author(s): 猪口大輔
  • Organizer: 日本化学会第90春季年会
  • Place of Presentation: 近畿大学(大阪)
• [Presentation] テトラキス(2-ピリジル)メタン骨格を基盤とする新規配位子の合成 (2010)
  • Author(s): 川下和晃
  • Organizer: 日本化学会第90春季年会
  • Place of Presentation: 近畿大学(大阪)
• [Presentation] フェニル・ピラジニル-(2-ピリジル)-(2-ピリミジニル)メタンの合成と光学的性質 (2010)
  • Author(s): 三木香
  • Organizer: 日本化学会第90春季年会
  • Place of Presentation: 近畿大学(大阪)
• [Presentation] 銅イオンと錯形成するキラルなテトラアリールメタン誘導体の合成と物性 (2009)
  • Author(s): 松本幸三・三木香・平尾泰一・蔵田浩之・久保孝史
  • Organizer: 第3回有機π電子系シンポジウム
  • Place of Presentation: 別府杉乃井ホテル
  • Year and Date: 2009-12-04
• [Presentation] Chiral Tetraarylmethane Derivatives : Possible Bridging Ligands for Chiral Magnets (2009)
  • Author(s): K.Matsumoto, K.Miki, T.Inagaki, D.Inokuchi, Y.Hirao, H.Kurata, T.Kubo
  • Organizer: The Third Japanese-Russian Workshop on Open Shell Compounds and Molecular Spin Devices
  • Place of Presentation: 淡路ウェスティンホテル
  • Year and Date: 2009-11-17
• [Presentation] Tetrahedral Oligothiophenes : Synthesis, Structure and Optical Properties of Highly Symmetrical Oligothiophenes (2009)
  • Author(s): K.Matsumoto, S.Kugo, Y.Hirao, H.Kurata, T.Kubo
  • Organizer: The 11th International Kyoto Conference on New Aspects of Organic Chemistry (IKCOC-11)
  • Place of Presentation: 京都リーガロイヤルホテル
  • Year and Date: 2009-11-12
• [Presentation] 末端にヘキシル基を有する正四面体型拡張オリゴチオフェン類の合成、構造および物性 (2009)
  • Author(s): 久後聡太・松本幸三・平尾泰一・蔵田浩之・久保孝史
  • Organizer: 第20回基礎有機化学討論会
  • Place of Presentation: 群馬大学
  • Year and Date: 2009-09-29
• [Presentation] キレート効果を有するキラルなテトラアリールメタン類の合成と物性 (2009)
  • Author(s): 三木香・松本幸三・根平達夫・Gennaro Pescitelli・平尾泰一・蔵田浩之・久保孝史
  • Organizer: 第20回基礎有機化学討論会,
  • Place of Presentation: 群馬大学
  • Year and Date: 2009-09-29
• [Presentation] Synthesis of Trimethylenemethane (TMM) Derivatives Extended with Pyridine Rings (2009)
  • Author(s): K.Matsumoto, D.Inokuchi, Y.Hirao, H.Kurata, K.Sato, T.Takui, T.Kubo
  • Organizer: ISNA-13 Satellite meeting "Diradical and Multiradicals: Theory and Experiment"
  • Place of Presentation: ナミュール,ベルギー
  • Year and Date: 2009-07-21
• [Presentation] Synthesis, X-ray analysis and optoelectronic properties of tetrahedral oligothiophenes (2009)
  • Author(s): K.Matsumoto, S.Kugo, Y.Hirao, H.Kurata, T.Kubo
  • Organizer: The 13th International Symposium on Novel Aromatic Compounds (ISNA-13)
  • Place of Presentation: ルクセンブルグ
  • Year and Date: 2009-07-21
• [Presentation] Synthesis, X-ray analysis and optoelectronic properties of tetrahedral oligothiophenes (2009)
  • Author(s): Kouzou Matsumoto
  • Organizer: The 13th International Symposium on Novel Aromatic Compounds (ISNA-13)
  • Place of Presentation: Luxembourg
• [Presentation] Synthesis of trimethylenemethane (TMM) derivatives extended with pyridine rings (2009)
  • Author(s): Kouzou Matsumoto
  • Organizer: ISNA-13 Satellite meeting "Diradicals and Multiradicals : Theory and Experiment"
  • Place of Presentation: Namur, Belgium
• [Presentation] キレート効果を有するキラルなテトラアリールメタン類の合成と物性 (2009)
  • Author(s): 三木香
  • Organizer: 第20回基礎有機化学討論会
  • Place of Presentation: 群馬大学
• [Presentation] Tetrahedral Oligothiophenes : Synthesis, Structure and Optical Properties of Highly Symmetrical Oligothiophenes (2009)
  • Author(s): Kouzou Matsumoto
  • Organizer: The 11th International Kyoto Conference on New Aspects of Organic Chemistry (IKCOC-11)
  • Place of Presentation: リガロイャルホテ・京都Kyoto, Japan
• [Presentation] Chiral Tetraarylmethane Derivatives : Possible Bridging Ligands for Chiral Magnets (2009)
  • Author(s): Kouzou Matsumoto
  • Organizer: The third Japanese-Russian Workshop on Open Shell Compounds and Molecular Spin Devices
  • Place of Presentation: Awaji Island, Japan
• [Presentation] 銅イオンと錯形成するキラルなテトラアリールメタン誘導体の合成と物性 (2009)
  • Author(s): 松本幸三
  • Organizer: 第3回有機π電子系シンポジウム
  • Place of Presentation: 杉乃井ホテル(別府・大分)