Integrated Synthesis of Polydiazo Compounds toward the Construction of Organic Magnets

2013 Fiscal Year Final Research Report

• Project Area: Organic Synthesis based on Integration of Chemical Reactions. New Methodologies and New Materials
• Project/Area Number: 21106013
• Research Category: Grant-in-Aid for Scientific Research on Innovative Areas (Research in a proposed research area)
• Allocation Type: Single-year Grants
• Review Section: Science and Engineering
• Research Institution: Mie University
• Principal Investigator: KITAGAWA Toshikazu 三重大学, 工学(系)研究科(研究院), 教授 (20183791)
• Co-Investigator(Kenkyū-buntansha): HIRAI Katsuyuki 三重大学, 社会連携研究センター, 准教授 (80208793)
• Co-Investigator(Renkei-kenkyūsha): OKAZAKI Takao 三重大学, 大学院工学研究科, 准教授 (90301241)
• Project Period (FY): 2009-07-23 – 2014-03-31
• Keywords: 有機磁性体 / 三重項カルベン / 高スピンポリカルベン / ジアゾメタン / 薗頭カップリング / デンドリマー / イオン液体

Research Abstract

Polycarbenes generated from properly-designed polydiazo precursors represent potential components for organic magnets. To construct high-spin polycarbenes, the spins of the component carbene units should interact ferromagnetically. In this study, sterically protected poly(diaryldiazomethanes) were synthesized by integrated reaction, and the properties of the corresponding carbenes were studied.

Research Products

• [Journal Article] Single Molecule Study of the Electronic Structures of Molecular Tripods with Functional Units (2014)
  • Author(s): Satoshi Katano, Yousoo Kim, Toshikazu Kitagawa, Maki Kawai
  • Journal Title: J. Vac. Soc. Jpn Volume: 57 Pages: 159-162
  • DOI: 10.3131/jvsj2.57.159
  • Peer Reviewed
• [Journal Article] Tailoring Electronic States of a Single Molecule Using Adamantane-based Molecular Tripods (2013)
  • Author(s): Satoshi Katano, Yousoo Kim, Toshikazu Kitagawa, Maki Kawai
  • Journal Title: Phys. Chem. Chem. Phys Volume: 15 Pages: 14229-14233
  • DOI: 10.1039/c3cp51612a
  • Peer Reviewed
• [Journal Article] NMR and DFT Study on Onium Ions Derived from Substituted Fluoranthenes and Benzo[k]fluoranthenes (2013)
  • Author(s): Takao Okazaki, Taisuke Adachi, Toshikazu Kitagawa
  • Journal Title: Bull. Chem. Soc. Jpn Volume: 86 Pages: 464-471
  • DOI: 10.1021/la305092g
  • Peer Reviewed
• [Journal Article] Ideal Redox Behavior of the High-Density Self-Assembled Monolayer of a Molecular Tripod on a Au(111) Surface with a Terminal Ferrocene Group (2013)
  • Author(s): Toshikazu Kitagawa, Hiroaki Matsubara, Koichi Komatsu, Katsuyuki Hirai, Takao Okazaki, Takahiro Hase
  • Journal Title: Langmuir Volume: 29 Pages: 4275-4282
  • DOI: 10.1021/la305092g
  • Peer Reviewed
• [Journal Article] Generation and Reactivities of Triplet Diphenylcarbenes Protected by Bulky Groups as para Substituents (2011)
  • Author(s): Katsuyuki Hirai, Keiji Hatanaka, Tsuyoshi Yamaguchi, Akiko Miyajima, Toshikazu Kitagawa, and Hideo Tomioka
  • Journal Title: J. Phys. Org Volume: 24 Pages: 909-920
  • DOI: 10.1002/poc.1898
  • Peer Reviewed
• [Journal Article] Allyl Radical Nature of a Phenylcyclopentadienyl Radical Annelated with Two Homoadamantene Frameworks (2011)
  • Author(s): Kohei Ogawa, Koichi Komatsu, and Toshikazu Kitagawa
  • Journal Title: J. Org. Chem Volume: 76 Pages: 6095-6100
  • DOI: 10.1021/jo200748m
  • Peer Reviewed
• [Journal Article] Cyclobutadieneiron Tricarbonyl Annelated with Homoadamantene Frameworks (2011)
  • Author(s): Shinya Minegishi, Koichi Komatsu, and Toshikazu Kitagawa
  • Journal Title: Organometallics Volume: 30 Pages: 1002-1007
  • DOI: 10.1021/om101054d
  • Peer Reviewed
• [Journal Article] Self-Sensitized Photooxygenation of a C_<60>-Cycloheptatriene Dyad to Form Norcaradiene-Derived Endoperoxides (2010)
  • Author(s): Masaaki Hanamura, Jun Kamada, Akiyo Amano, Ken'ichi Takeuchi, Takao Okazaki, Katsuyuki Hirai, and Toshikazu Kitagawa
  • Journal Title: Eur. J. Org. Chem Pages: 3257-3264
  • DOI: 10.1002/ejoc.200901453
  • Peer Reviewed
• [Journal Article] Triplet Diphenylcarbene Protected by Iodine and Bromine Groups (2010)
  • Author(s): Katsuyuki Hirai, Kana Bessho, Toshikazu Kitagawa, and Hideo Tomioka
  • Journal Title: J. Phys. Org. Chem Volume: 23 Pages: 347-356
  • DOI: 10.1002/poc.1651
  • Peer Reviewed
• [Journal Article] Stable-Ion NMR Spectroscopy and GIAO-DFT Study of Carbocations Derived from Multibridged [3n]Cyclophanes (2009)
  • Author(s): Kenneth K. Laali, Takao Okazaki, Toshikazu Kitagawa, and Teruo Shinmyozu
  • Journal Title: Eur. J. Org. Chem Pages: 4451-4457
  • DOI: 10.1002/ejoc.200900479
  • Peer Reviewed
• [Presentation] イオン液体を用いた薗頭カップリングの反応集積化による1,3,5-トリス[(4-ベンゾイルフェニル)エチニル]ベンゼンとその誘導体の合成 (2014)
  • Author(s): 林賢之介、吉川世里奈、岡崎隆男、北川敏一
  • Organizer: 日本化学会第94春季年会
  • Place of Presentation: 名古屋大学東山キャンパス
  • Year and Date: 2014-03-28
• [Presentation] 巨大置換基によって保護された三重項(9-アントリル)(アリール)カルベンの特性化と反応性 (2014)
  • Author(s): 橋本裕一、館 美里、平井克幸、北川敏一
  • Organizer: 日本化学会第94春季年会
  • Place of Presentation: 名古屋大学東山キャンパス
  • Year and Date: 2014-03-27
• [Presentation] Generation, Characterization and Reactivity of Triplet Diphenylcarbene Protected by Four Iodine Groups (2013)
  • Author(s): Katsuyuki Hirai, Kosaku Tsujita, Kana Bessho, Toshikazu Kitagawa
  • Organizer: The 8th International Symposium on Integrated Synthesis (ISIS-8)
  • Place of Presentation: 奈良市東大寺総合文化センター
  • Year and Date: 2013-11-30
• [Presentation] ヨード基とトリフルオロメチル基によって保護された三重項ジフェニルカルベンの発生と特性化 (2013)
  • Author(s): 田村まり、平井克幸、北川敏一
  • Organizer: 2013 年有機反応機構研究会
  • Place of Presentation: 三重大学
  • Year and Date: 2013-09-26
• [Presentation] Reaction Integration of Sonogashira Couplings for Synthesis of Substituted 1,3,5-Tris[(4-benzoylphenyl)-ethynyl]benzenes in Ionic Liquid (2013)
  • Author(s): Kennosuke Hayashi, Takao Okazaki, Toshikazu Kitagawa
  • Organizer: The 3rd International Symposium for Sustainability by Engineering at MIU
  • Place of Presentation: 三重大学
  • Year and Date: 2013-09-17
• [Presentation] Self-assembled Monolayers of Ferrocene Bound to Au(111) Surface through Tripodhaped Trithiol and Oligo(p-phenyleneethynylene) Bridge (2012)
  • Author(s): Toshikazu Kitagawa, Takahiro Hase, Toshiki Tanaka, Hisashi Umemura
  • Organizer: The 12th International Kyoto Conference on New Aspects of Organic Chemistry (IKCOC-12)
  • Place of Presentation: リーガロイヤルホテル京都(京都市)
  • Year and Date: 2012-11-14
• [Presentation] フローマイクロリアクター中での長寿命三重項ジフェニルカルベンの発生と反応制御 (2012)
  • Author(s): 沖殿航紀、栗田 翔、平井克幸、北川敏一
  • Organizer: 第23回基礎有機化学討論会
  • Place of Presentation: 京都テルサ(京都市)
  • Year and Date: 2012-09-20
• [Presentation] 立体保護基によって長寿命化した三重項ジアリールカルベンの発生、特性化と反応性 (2012)
  • Author(s): 平井克幸、辻田耕作、別所香菜、山口正雄、北川敏一
  • Organizer: 第23回基礎有機化学討論会
  • Place of Presentation: 京都テルサ(京都市)
  • Year and Date: 2012-09-19
• [Presentation] Generation and Reactivity of Triplet Diphenylcarbene Protected (2011)
  • Author(s): Kosaku Tsujita, Kana Bessho, Katsuyuki Hirai, Toshikazu Kitagawa, Hideo Tomioka
  • Organizer: Four Iodine Groups International Symposium for Sustainability by Engineering at MIU
  • Place of Presentation: 三重大学
  • Year and Date: 2011-12-02
• [Presentation] イミダゾリウム系イオン液体中でのソルボリシス、脱ジアゾ環化反応、および連続した薗頭カップリング反応 (2011)
  • Author(s): 岡崎隆男、伊藤弘二、山本祐之、北川敏一
  • Organizer: 第22回基礎有機化学討論会
  • Place of Presentation: つくば国際会議場
  • Year and Date: 2011-09-23
• [Presentation] 三重項( アリール)(1,4- ジフェニル-1H-1,2,3-トリアゾール-5-イル)カルベンの発生と反応性 (2011)
  • Author(s): 平井克幸、山口正雄、北川敏一、富岡秀雄
  • Organizer: 2011年光化学討論会
  • Place of Presentation: 宮崎市河畔コンベンションエリア
  • Year and Date: 2011-09-06
• [Presentation] Self-assembled Monolayers of Dyads Consisting of Tripod-shaped Trithiol and Ferrocene on Au(111) (2010)
  • Author(s): Toshikazu Kitagawa
  • Organizer: 2010 International Chemical Congress of Pacific Basin Societies (PACIFICHEM 2010)
  • Place of Presentation: Honolulu, U.S.A.
  • Year and Date: 2010-12-19
• [Presentation] Persistent triplet diphenylcarbenes: Steric protection by ortho- orpara-substituents (2010)
  • Author(s): Katsuyuki Hirai, Toshikazu Kitagawa, Hideo Tomioka
  • Organizer: 2010 International Chemical Congress of Pacific Basin Societies (PACIFICHEM 2010)
  • Place of Presentation: Honolulu, U.S.A.
  • Year and Date: 2010-12-18
• [Presentation] オリゴ(p-フェニレンエチニレン)をリンカーとする三脚形トリチオール‐フェロセン連結体のAu 基板上における単分子膜の電気化学特性 (2010)
  • Author(s): 北川敏一、平井克幸、長谷隆啓、田中敬規、早川幾麻
  • Organizer: 第21回基礎有機化学討論会
  • Place of Presentation: 名古屋大学東山キャンパス
  • Year and Date: 2010-09-11
• [Presentation] 立体的に混雑したジフェニルジアゾメタンの薗頭カップリング反応によるポリ(ジアゾ)化合物の合成とその光分解によって発生するポリカルベンの特性化 (2010)
  • Author(s): 新宅雅哉、平井克幸、北川敏一、富岡秀雄
  • Organizer: 第21回基礎有機化学討論会
  • Place of Presentation: 名古屋大学東山キャンパス
  • Year and Date: 2010-09-10
• [Presentation] 4つのヨード基によって保護された三重項ジフェニルカルベンの発生と反応性 (2010)
  • Author(s): 平井克幸、別所香菜、北川敏一、富岡秀雄
  • Organizer: 2010年光化学討論会
  • Place of Presentation: 千葉大学西千葉キャンパス
  • Year and Date: 2010-09-08
• [Presentation] パラ位巨大置換基に保護された三重項ジフェニルカルベンの反応制御―トリプチシル基の効果 (2010)
  • Author(s): 畑中啓司、平井克幸、北川敏一、富岡秀雄
  • Organizer: 日本化学会第90春季年会
  • Place of Presentation: 近畿大学本部キャンパス
  • Year and Date: 2010-03-27
• [Presentation] Stable-Ion and GIAO-DFT Study of Carbocations Derived From Multi-bridged [3n] (n = 3, 4, and 5) Cyclophanes (2009)
  • Author(s): Takao Okazaki, Toshikazu Kitagawa, Teruo Shinmyozu, Kenneth K. Laali
  • Organizer: 12th Kyushu International Symposium on Physical Organic Chemistry (KISPOC-12)
  • Place of Presentation: 九州大学
  • Year and Date: 2009-12-16
• [Presentation] A Dyad Consisting of Tripod-shaped Trithiol and Ferrocene: Preparation and Electrochemical Property of Self-assembled Monolayer on Au(111) (2009)
  • Author(s): Toshikazu Kitagawa
  • Organizer: 12th Kyushu International Symposium on Physical Organic Chemistry (KISPOC-12)
  • Place of Presentation: 九州大学
  • Year and Date: 2009-12-16
• [Presentation] 多架橋[3n]シクロファンのプロトン化によって生じたカルボカチオンのNMR 観測とDFT 計算 (2009)
  • Author(s): 岡崎隆男、北川敏一、新名主輝男、LaaliKenneth K
  • Organizer: 第20回基礎有機化学討論会
  • Place of Presentation: 群馬大学工学部桐生キャンパス
  • Year and Date: 2009-09-30
• [Remarks]
  • URL: http://www.ocm.chem.mie-u.ac.jp/web/