Syntheses of compounds with ultralong C-C bond and investigation of their diradical character

• Project/Area Number: 24750032
• Research Category: Grant-in-Aid for Young Scientists (B)
• Allocation Type: Multi-year Fund
• Research Field: Organic chemistry
• Research Institution: Tohoku University
• Principal Investigator: TAKEDA Takashi 東北大学, 多元物質科学研究所, 助教 (80625038)
• Project Period (FY): 2012-04-01 – 2014-03-31
• Project Status: Completed (Fiscal Year 2013)
• Budget Amount: ¥4,680,000 (Direct Cost: ¥3,600,000、Indirect Cost: ¥1,080,000); Fiscal Year 2013: ¥1,950,000 (Direct Cost: ¥1,500,000、Indirect Cost: ¥450,000); Fiscal Year 2012: ¥2,730,000 (Direct Cost: ¥2,100,000、Indirect Cost: ¥630,000)
• Keywords: 長い結合 / X線結晶構造解析 / サーモクロミズム / ジラジカル / ＤＦＴ計算 / ヘキサフェニルエタン / アセナフチレン / X線構造解析

Research Abstract

Examination of physical properties of compounds with an ultralong C-C bond and investigation of molecules with a further elongated C-C bond were conducted. Thermochromism phenomenon was observed in bis(acridan) with pyracene scaffold both in the crystalline and powder states. DFT calculation suggested longer C-C bond might be found when more rigid scaffold is used. Molecular design for elongation of C-C bond was applied to C=C double bond to prepare compounds with a long C=C bond.

Research Products

• [Journal Article] Preparation and structure of acenaphthylene-1,2-diyldi(9-acridine) with a long C=C bond (2014)
  • Author(s): Takashi Takeda, Yasuto Uchimura, Hidetoshi Kawai, Ryo Katoono, Kenshu Fujiwara, Takanori Suzuki
  • Journal Title: Chemical Communications Volume: 50 Issue: 30 Pages: 3924-3927
  • DOI: 10.1039/c3cc49573f
  • Peer Reviewed / Open Access
• [Journal Article] Chiral memory units based on dynamic redox systems with a dibenzoxepinone skeleton : Drastic change in racemization barrier and clectrochemical bistability (2014)
  • Author(s): Kazuhisa Wada, Yuna Chiba, Takashi Takeda, Hidetoshi Kawai, Ryo Katoono, Kenshu Fujiwara, Takanori Suzuki
  • Journal Title: Heterocycles Volume: 88 Issue: 2 Pages: 945-952
  • DOI: 10.3987/com-13-s(s)93
  • Peer Reviewed
• [Journal Article] Expandability of ultralong C-C bond : Largely different C_1-C_2 bond length determined by low-temperature X-ray structural analyses on pseudopolymorphs of 1,1-Bis(4-fluorophenyl)-2,2-bis(4-methoxyp henyl)pyracene (2014)
  • Author(s): Takanori Suzuki, Yasuto Uchimura, Takashi Takeda, Hidetoshi Kawai, Ryo Katoono, Kenshu Fujiwara, Kei Murakoshi, Takanori Fukushima, Aiichiro Nagaki, Junichi Yoshida
  • Journal Title: Chemistry Letters Volume: 43 Issue: 1 Pages: 86-88
  • DOI: 10.1246/cl.130872
  • NAID: 130004427101
  • Peer Reviewed / Open Access
• [Journal Article] Multi-Functional Molecular Rotators with Dielectric, Magnetic and Optical Responses (2013)
  • Author(s): Norihisa Hoshino,* Takashi Takeda, and Tomoyuki Akutagawa*
  • Journal Title: RSC Advance Volume: 4 Issue: 2 Pages: 743-747
  • DOI: 10.1039/c3ra44515a
  • Peer Reviewed
• [Journal Article] Geometrical Remote Steric Effects in 4,5-Disubsltituted-9,10-dihydrophenanthrenes : Expansion of Prestrained C^9-C^<10> Bond in Di (spiroacridan) Derivatives (2013)
  • Author(s): Kazuhisa Wada, Takashi Takeda, Hidetoshi Kawai, Ryo Katoono, Kenshu Fujiwara, Takanori Suzuki
  • Journal Title: Chemistry Letters Volume: 42 Issue: 10 Pages: 1244-1246
  • DOI: 10.1246/cl.130502
  • NAID: 10031201307
  • Peer Reviewed
• [Journal Article] Hexaphenylethanes with an Ultralong C&ndash;C Bond: Expandability of the C&ndash;C Bond in Highly Strained Tetraarylpyracenes (2013)
  • Author(s): T. Takeda, Y. Uchimura, H. Kawai, R. Katoono, K. Fujiwara, T. Suzuki
  • Journal Title: Chemistry Letters Volume: 42 Issue: 9 Pages: 954-962
  • DOI: 10.1246/cl.130598
  • NAID: 10031194306
  • ISSN: 0366-7022, 1348-0715
  • Peer Reviewed
• [Journal Article] Synthesis and Structure of 1,4,5,8-Tetraethynylnaphthalene Derivatives (2012)
  • Author(s): Takashi Takeda, Yoshito Tobe
  • Journal Title: Chem. Commun Volume: 48 Issue: 63 Pages: 7841-7843
  • DOI: 10.1039/c2cc33740a
  • Peer Reviewed
• [Journal Article] Nonadditive substituent effects on expanding prestrained C-C bond in crystal : X-ray analyses on unsymmetrically substituted tetraarylpyracenes prepared by a flow microreactor method (2012)
  • Author(s): Takanori Suzuki, Yasuto Uchimura, Yusuke Ishigaki, Takashi Takeda, Ryo Katoono, Hidetoshi Kawai, Kenshu Fujiwara, Aiichiro Nagaki, Junichi Yoshida
  • Journal Title: Chemistry Letters Volume: 41 Pages: 541-543
  • NAID: 10030619852
  • Peer Reviewed
• [Journal Article] Nonadditive substituent effects on expanding prestrained c-c bond in crystal: X-ray analyses on unsymmetrically substituted tetraarylpyracenes prepared by a flow microreactor method (2012)
  • Author(s): Yusuke Ishigaki, et a1.
  • Journal Title: Chemistry Letters Volume: 41 Issue: 5 Pages: 541-543
  • DOI: 10.1246/cl.2012.541
  • NAID: 10030619852
  • Peer Reviewed
• [Presentation] ジシアノメチレン基を導入したキナクリドン誘導体の動的挙動とエレクトロクロミズム (2014)
  • Author(s): 武田貴志, 芥川智行
  • Organizer: 日本化学会第94春季年会
  • Place of Presentation: 名古屋大学
  • Year and Date: 2014-03-28
• [Presentation] Preparation and properties of quinoxaline based electron acceptor (2013)
  • Author(s): Takashi Takeda, Tomoyuki Akutagawa
  • Organizer: International symposium for the 70^<th >anniversary of the Tohoku branch of the chemical society of japan
  • Place of Presentation: 東北大学
  • Year and Date: 2013-09-29
• [Presentation] ジシアノメチレン基が置換したキナクリドン誘導体の構造と光物性 (2013)
  • Author(s): 武田貴志, 杉原寛之, 富永亮, 鈴木康孝, 川俣純, 芥川智行
  • Organizer: 第24回基礎有機化学討論会
  • Place of Presentation: 学習院大学
  • Year and Date: 2013-09-06
• [Presentation] アセナフチレン-1,2-ジイルジ(9-アクリジン)誘導体で認められる長いC=C結合 (2013)
  • Author(s): 武田貴志, 内村康人, 上遠野亮, 河合英敏, 藤原憲秀, 鈴木孝紀
  • Organizer: 第24回基礎有機化学討論会
  • Year and Date: 2013-09-05
• [Presentation] Molecular structure and photophysical properties of quinacridone and acridone based electron acceptors (2013)
  • Author(s): Takashi Takeda, Makoto Tominaga, Yasutaka Suzuki, Jun Kawamata, Tomoyuki Akutagawa
  • Organizer: 15^<th> International symposium on novel aromatic compounds
  • Place of Presentation: Taipei, Taiwan
  • Year and Date: 2013-08-01
• [Presentation] Liquid crystalline n-type semiconductor : Dicyanopyrazinoquinoxaline with long alkoxy chains (2013)
  • Author(s): Takashi Takeda, Tomoyuki Akutagawa
  • Organizer: The 11^<th> international symposium on functional π-electronic systems
  • Place of Presentation: Arcachon, France
  • Year and Date: 2013-06-03
• [Presentation] 電子受容性を有する長鎖アルコキシ置換ジシアノピラジノキノキサリンの合成と物性 (2013)
  • Author(s): 武田貴志, 芥川智行
  • Organizer: 日本化学会第93春季年会
  • Place of Presentation: 立命館大学
  • Year and Date: 2013-03-25
• [Presentation] ビス(スピロアクリダン)置換ジヒドロフェナントレンのC_9-C_<10 >結合 : 骨格のねじれと結合長の相間 (2013)
  • Author(s): 和田和久, 葭本泰代, 太田賢司, 河合英敏, 武田貴志, 上遠野亮, 藤原憲秀, 鈴木孝紀
  • Organizer: 日本化学会第93春季年会
  • Place of Presentation: 立命館大学
  • Year and Date: 2013-03-23
• [Presentation] Preparation and properties of quinoxaline based electron acceptor (2013)
  • Author(s): Takashi Takeda, Tomoyuki Akutagawa
  • Organizer: International Symposium for the 70th Annivarsary of the Tohoku Branch of the Chemical Society of Japan
  • Place of Presentation: Sendai, Japan
• [Presentation] ジシアノメチレン基が置換したキナクリドン誘導体の構造と光物性 (2013)
  • Author(s): 武田 貴志、杉原 寛之、富永 亮、鈴木 康孝、川俣 純、芥川 智行
  • Organizer: 第２４回基礎有機化学討論会
  • Place of Presentation: 学習院大学
• [Presentation] アセナフチレン-1,2-ジイルジ(9-アクリジン)誘導体で認められる長いC=C 結合 (2013)
  • Author(s): 武田 貴志、内村 康人、上遠野 亮、河合 英敏、藤原 憲秀、鈴木 孝紀
  • Organizer: 第２４回基礎有機化学討論会
  • Place of Presentation: 学習院大学
• [Presentation] 長鎖アルコキシ置換ジシアノピラジノキノキサリンが形成する液晶・ナノミセル (2013)
  • Author(s): 武田 貴志、星野 哲久、芥川 智行
  • Organizer: 第７回分子科学討論会
  • Place of Presentation: 京都テルサ
• [Presentation] Molecular Structure and Photophysical Properties of Quinacridone and Acridone Based Electron Acceptors (2013)
  • Author(s): Takashi Takeda, Makoto Tominaga, Yasutaka Suzuki, Jun Kawamata, Tomoyuki Akutagawa
  • Organizer: 15th International Symposium on Novel Aromatic Compounds
  • Place of Presentation: Taipei, Taiwan
• [Presentation] Liquid crystalline n-type semiconductor: Dicyanopyrazinoquinoxaline derivative with long alkoxy chains (2013)
  • Author(s): Takashi Takeda, Tomoyuki Akutagawa
  • Organizer: The 11th International Symposium on Functional π-electron systems
  • Place of Presentation: Arcachon, France
• [Presentation] 電子受容性を有する長鎖アルコキシ置換ジシアノピラジノキノキサリンの合成と物性 (2013)
  • Author(s): 武田 貴志、芥川 智行
  • Organizer: 日本化学会第９３春季年会
  • Place of Presentation: 滋賀県草津市
• [Presentation] ビス(スピロアキルダン)置換ジヒドロフェナントレンのC9-C10結合：骨格のねじれと結合長の相関 (2013)
  • Author(s): 和田 和久、葭本 泰代、太田 賢司、河合 英敏、武田 貴志、上遠野 亮、藤原 憲秀、鈴木 孝紀
  • Organizer: 日本化学会第９３春季年会
  • Place of Presentation: 滋賀県草津市
• [Presentation] 長鎖アルコキシ置換ジシアノピラジノキノキサリンが形成する液晶・ナノミセル (2012)
  • Author(s): 武田貴志, 星野哲久, 芥川智行
  • Organizer: 第7回分子科学討論会
  • Place of Presentation: 京都テルサ
  • Year and Date: 2012-09-27
• [Presentation] Synthesis of tetraazaacenes having four alkyl of amide chains (2012)
  • Author(s): Takashi Takeda, Tomoyuki Akutagawa
  • Organizer: International conference on science and technology of scynthetic metals (ICSM 2012)
  • Place of Presentation: Atlanta, GA, USA
  • Year and Date: 2012-07-10
• [Presentation] Synthesis of tetraazaacenes having four alkyl or amide chains (2012)
  • Author(s): Takashi Takeda, Tomoyuki Akutagawa
  • Organizer: International Conference on Science and Technology of Synthetic Metals (ICSM2012)
  • Place of Presentation: Atlanta, GA, USA