Synthesis of unusual conducting nano-ribbons by catenating non-planar singlet biradicals

• Project/Area Number: 22350058
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Functional materials chemistry
• Research Institution: Tokyo Institute of Technology
• Principal Investigator: ITO Shigekazu 東京工業大学, 大学院・理工学研究科, 准教授 (00312538)
• Project Period (FY): 2010 – 2012
• Project Status: Completed (Fiscal Year 2012)
• Budget Amount: ¥18,720,000 (Direct Cost: ¥14,400,000、Indirect Cost: ¥4,320,000); Fiscal Year 2012: ¥2,860,000 (Direct Cost: ¥2,200,000、Indirect Cost: ¥660,000); Fiscal Year 2011: ¥3,120,000 (Direct Cost: ¥2,400,000、Indirect Cost: ¥720,000); Fiscal Year 2010: ¥12,740,000 (Direct Cost: ¥9,800,000、Indirect Cost: ¥2,940,000)
• Keywords: 電気 / 磁気的機能 / 一重項ビラジカル / 複素環化学 / 結晶構造 / 有機エレクトロニクス / 電気・磁気的機能 / 電気化学 / 超分子 / 有機元素化学 / 複素環構造 / 酸化還元特性 / 有機典型元素化学 / 静電相互作用 / 結晶構造解析 / 電荷移動錯体

Research Abstract

Highly stabilized localized biradicals composed of the four-membered phosphorus heterocycle skeleton possess three-dimensional characteristics and exhibit remarkably high electron-donating ability. In this project we examined molecular design and synthesis of oligo(biradicals) using catenation of the P-heterocyclic biradical units, which induces through-space electrostatic intramolecular interaction. Characterization of the corresponding mixed-valent radical cations upon oxidation was also performed.

Research Products

• [Journal Article] Through-space Electrostatic Interaction between the Electron-donating 1,3-Diphospha- cyclobutane-2,4-diyl Units (2013)
  • Author(s): Shigekazu Ito, Makoto Kobayashi, Koichi Mikami
  • Journal Title: Org. Lett. Volume: Vol. 15 Issue: 13 Pages: 3404-3407
  • DOI: 10.1021/ol401456h
  • Peer Reviewed
• [Journal Article] Trang Thi Thu Ngo Koichi Mikami, Silyl Effects on 1,3-Diphospha- cyclobutane-2,4-diyl: Ring-Opening of Tetra- hydrofuran and Promotion of Reductive P-C Cleavage (2013)
  • Author(s): Shigekazu Ito
  • Journal Title: Chem.Asian J. Volume: Vol.8 Issue: 9 Pages: 1976-1980
  • DOI: 10.1002/asia.201300564
  • Peer Reviewed
• [Journal Article] 高安定性リン複素環一重項ビラジカルおよび関連分子系の合成と性質 (2012)
  • Author(s): 伊藤繁和
  • Volume: Vol.70、No7
  • Pages: 731-741
  • Peer Reviewed
• [Journal Article] 高安定性リン複素環一重項ビラジカルおよび関連分子系の合成と性質 (2012)
  • Author(s): 伊藤繁和
  • Journal Title: 有機合成化学協会誌 Volume: 70 Pages: 731-741
  • Peer Reviewed
• [Journal Article] Spectroscopic and stability studies on unsymmetrical 1,3-dialkyl-1,3- diphosphacyclobutane-2,4-diyls (2012)
  • Author(s): S. Ito, M. Kikuchi, J. Miura, N. Morita, M. Yoshifuji
  • Journal Title: J. Phys. Org. Chem. Volume: 25 Issue: 9 Pages: 733-737
  • DOI: 10.1002/poc.1957
  • Peer Reviewed
• [Journal Article] Unique molecular distortion in the 2,4,6-tri-t-butylphenyl group (2012)
  • Author(s): S. Ito, H. Miyake, M. Yoshifuji
  • Journal Title: ARKIVOC Volume: 2012 Pages: 6-14
  • Peer Reviewed
• [Journal Article] New Aspects of 1,3-Diphosphacyclobutane-2,4-diyls (2012)
  • Author(s): M. Yoshifuji, Y. Hirano, G. Schnakenburg, R. Streubel, E. Niecke, S. Ito
  • Journal Title: Helv. Chim. Acta Volume: 95 Issue: 10 Pages: 1723-1729
  • DOI: 10.1002/hlca.201200442
  • Peer Reviewed
• [Journal Article] Umpolung of Fluoroform by C-F Bond Activation: Direct Difluoromethylation of Lithium Enolates (2012)
  • Author(s): T. Iida, R. Hashimoto, K. Aikawa, S. Ito, K. Mikami
  • Journal Title: Angew. Chem. Int. Ed. Volume: 51 Issue: 38 Pages: 9535-9538
  • DOI: 10.1002/anie.201203588
  • Peer Reviewed
• [Journal Article] Direct Preparation of Trifluoromethylindium Reagents from Trifluoromethyl Iodide: Effective Trifluoromethylation and Perfluoroalkylation Reagents (2012)
  • Author(s): M. Fujiu, Y. Nakamura, H. Serizawa, K. Aikawa, S. Ito, K. Mikami
  • Journal Title: Eur. J. Org. Chem. Volume: 2012 Issue: 36 Pages: 7043-7047
  • DOI: 10.1002/ejoc.201201116
  • Peer Reviewed
• [Journal Article] Combination of sp2-and sp3-Type Phosphorus Atoms for Gold Chemistry : Preparation, Structure, and Catalytic Activity of Gold Complexes That Bear Ligated 2-Sily1-1,3-diphosphapropenes (2011)
  • Author(s): S.Ito, L.Zhai, K.Mikami
  • Journal Title: Chem.Asian J. Volume: 6 Issue: 11 Pages: 3077-3083
  • DOI: 10.1002/asia.201100310
  • Peer Reviewed
• [Journal Article] [2,3]WITTIG REARRANGEMENT OF '-HYDROXYETHYL BISALLYLIC ETHERS : HIGHLY REGIOSPECIFIC ENTRY TO SINGLY DEHYDROXYLATED 19-NOR-1(OR 3),25-DIHYDROXYVITAMIN D3 (2011)
  • Author(s): K.Mikami, K.Fujita, K.Wakabayashi, S.Ito
  • Journal Title: Heterocycles Volume: 82 Issue: 2 Pages: 1163-1170
  • DOI: 10.3987/com-10-s(e)111
  • Peer Reviewed
• [Journal Article] Intensive NMR Study of 1-t-Buty1-3-methy1-2,4-bis(2,4,6-tri-t-butylphenyl)-1,3-diphosphacyclobutane'2,4-diyl (2011)
  • Author(s): M.Yoshifuji, S.T.Osborn, A.J.Arduengo, III, K.A.Belmore, S.Ito
  • Journal Title: Heteroat.Chem Volume: 22 Pages: 331-338
  • Peer Reviewed
• [Journal Article] Ligand effect of bulky 2,2-dialkyl-1-phosphaethenes on Au-catalyzed cycloisomerization of 1,6-enynes and lactonization of pent-4-ynoic acids (2010)
  • Author(s): S.Ito, S.Kusano, N.Morita, K.Mikami, M.Yoshifuji
  • Journal Title: J.Organomet.Chem. Volume: 685 Pages: 291-296
  • Peer Reviewed
• [Journal Article] Highly enantioselective synthesis of a-(perfluoroalkyl)amines via hydrogenation of enamide precursors in the presence of chiraphos-rhodium catalyst (2010)
  • Author(s): K.Mikami, T.Murase, L.Zhai, Y.Itoh, S.Ito
  • Journal Title: Tetrahedron : Asymmetry Volume: 21 Pages: 1158-1161
  • Peer Reviewed
• [Journal Article] Synthesis and physicochemical properties of stable 1,3-diphosphacyclobutane-2,4-diyls bearing sulfanyl groups (2010)
  • Author(s): S.Ito, J.Miura, N.Morita, M.Yoshifuji, A.J.Arduengo
  • Journal Title: C.R.Chimie Volume: 13 Pages: 1180-1184
  • Peer Reviewed
• [Journal Article] Synthesis and physicochemical properties of stable 1,3-diphosphacyclobutane-2,4-diyls bearing sulfanyl groups (2010)
  • Author(s): S.Ito, J.Miura, N.Morita, M.Yoshifuji, A.J.Arduengo
  • Journal Title: Heteroat.Chem. Volume: 21 Pages: 404-411
  • Peer Reviewed
• [Journal Article] Diverse reactions of sterically-protected 1,3-diphosphacyclobutane-2,4-diyls with hydride (2010)
  • Author(s): S.Ito, J.Miura, N.Morita, M.Yoshifuji, A.J.Arduengo
  • Journal Title: Dalton Trans. Volume: 39 Pages: 8281-8287
  • Peer Reviewed
• [Presentation] トリアジン直結型リン複素環ビラジカル誘導体の合成および物性 (2013)
  • Author(s): 植田恭弘、三上幸一、伊藤繁和
  • Organizer: 日本化学会第93春季年会
  • Place of Presentation: 立命館大学びわこ・くさつキャンパス（滋賀県）
• [Presentation] DPCB-金錯体におけるカウンターアニオンの効果とキラルアニオンを用いた不斉反応への応用 (2013)
  • Author(s): 南口晋毅、三上幸一、相川光介、伊藤繁和
  • Organizer: 日本化学会第93春季年会
  • Place of Presentation: 立命館大学びわこ・くさつキャンパス（滋賀県）
• [Presentation] 炭素‐フッ素結合活性化を基盤とする金属エノラートに対するα－ジフルオロメチル化反応 (2013)
  • Author(s): 橋本涼太、飯田稔明、相川光介、伊藤繁和、三上幸一
  • Organizer: 日本化学会第93春季年会
  • Place of Presentation: 立命館大学びわこ・くさつキャンパス（滋賀県）
• [Presentation] 1,3-ジホスファシクロブタン-2,4-ジイルの結晶多形とFET特性 (2013)
  • Author(s): 伊藤繁和、小林誠、ゴ チャンティトゥ、植田恭弘、三上幸一、西田純一、山下敬郎
  • Organizer: 日本化学会第93春季年会
  • Place of Presentation: 立命館大学びわこ・くさつキャンパス（滋賀県）
• [Presentation] 空間相互作用を示すリン複素環ビラジカル連結体の構築 (2012)
  • Author(s): 伊藤繁和、小林誠、三上幸一
  • Organizer: 第39回有機典型元素化学討論会
  • Place of Presentation: いわて県民情報交流セン ター(岩手県)
  • Year and Date: 2012-12-08
• [Presentation] リン複素環ビラジカルのスピン多重度制御:含窒素複素環置換基を利用するアプローチ (2012)
  • Author(s): 植田恭弘、三上幸一、伊藤繁和
  • Organizer: 第101回有機合成シンポジウム、1-5
  • Place of Presentation: 慶應義塾大学薬学部(東京都)
  • Year and Date: 2012-06-06
• [Presentation] リン複素環ビラジカルのスピン多重度制御：含窒素複素環置換基を利用するアプローチ (2012)
  • Author(s): 植田恭弘、三上幸一、伊藤繁和
  • Organizer: 第101回有機合成シンポジウム
  • Place of Presentation: 慶應義塾大学薬学部（東京都）
• [Presentation] 31P-19F Hybrid for NMR Qubit Molecules (2012)
  • Author(s): S. Ito, T. Nakagawa, K. Mikami
  • Organizer: 10th International Conference on Heteroatom Chemistry (ICHAC-10)
  • Place of Presentation: 京都大学化学研究所、宇治（京都府）
• [Presentation] Phosphorus Version of the Fritsch-Buttenberg-Wiechell Reaction (2012)
  • Author(s): M. Yoshifuji, S. Ito
  • Organizer: 19th International Conference on Phosphorus Chemistry (ICPC 2012)
  • Place of Presentation: Rotterdam, The Netherlands
• [Presentation] 空間相互作用を示すリン複素環ビラジカル連結体の構築 (2012)
  • Author(s): 伊藤繁和、小林誠、三上幸一
  • Organizer: 第39回有機典型元素化学討論会
  • Place of Presentation: いわて県民情報交流センター、盛岡（岩手県）
• [Presentation] Tuning Catalytic Activity of Low-Coordinated Phosphaalkene-Gold(I) Complexes (2012)
  • Author(s): M. Nanko, K. Mikami, S. Ito
  • Organizer: 6th International Conference on Gold Science, Technology and Its Applications (Gold 2012)
  • Place of Presentation: 京王プラザホテル、新宿（東京都）
• [Presentation] フェニル置換対称型リン複素環ビラジカルの合成と性質 (2011)
  • Author(s): ゴチャンティトゥ、三上幸一、伊藤繁和
  • Organizer: 第38回有機典型元素化学討論会
  • Place of Presentation: 石川県立音楽堂邦楽ホール(石川県)
  • Year and Date: 2011-12-08
• [Presentation] フェニル置換対称型リン複素環ビラジカルの合成と性質 (2011)
  • Author(s): NGO Trang Thi Thu、三上幸一、伊藤繁和
  • Organizer: 第38回有機典型元素化学討論会
  • Place of Presentation: 金沢
  • Year and Date: 2011-12-08
• [Presentation] Sulfanyl-Substituted Air-Stable P-Heterocyclic Biradicals (2011)
  • Author(s): 伊藤繁和
  • Organizer: 開殼有機分子の合成と電子構造自由度に関する国際ワークショップ
  • Place of Presentation: 大阪
  • Year and Date: 2011-10-07
• [Presentation] 2-フルオロ-1,3-ジホスファプロペン誘導体の合成とNMR解析 (2011)
  • Author(s): 中川剛史、三上幸一、伊藤繁和
  • Organizer: 第35回フッ素化学討論会
  • Place of Presentation: 岡山大学
  • Year and Date: 2011-09-26
• [Presentation] 金属有機フッ素化学におけるパラダイムシフト (2011)
  • Author(s): 藤生基弘、芹澤宏希、中村雄三、橋本涼太、相川光介、伊藤繁和、三上幸一
  • Organizer: 第35回フッ素化学討論会
  • Place of Presentation: 岡山大学
  • Year and Date: 2011-09-26
• [Presentation] 直鎖状に配列した安定なリン複素環ビラジカルオリゴマーの合成と性質 (2011)
  • Author(s): 小林誠、三上幸一、伊藤繁和
  • Organizer: 第22回基礎有機化学討論会
  • Place of Presentation: 筑波大学(茨城県)
  • Year and Date: 2011-09-22
• [Presentation] 直鎖状に配列した安定なリン複素環ビラジカル_オリゴマーの合成と性質 (2011)
  • Author(s): 小林誠、三上幸一、伊藤繁和
  • Organizer: 第22回基礎有機化学討論会
  • Place of Presentation: つくば
  • Year and Date: 2011-09-22
• [Presentation] ねじれ型DPCB誘導体の合成と触媒活性 (2011)
  • Author(s): 南口晋毅、三上幸一、伊藤繁和
  • Organizer: 日本化学会第5回関東支部大会
  • Place of Presentation: 東京農工大学
  • Year and Date: 2011-08-30
• [Presentation] Redox Chemistry of Stable P-Heterocyclic Biradicals (2010)
  • Author(s): S.Ito
  • Organizer: 2010環太平洋国際化学会議(PACIFICHEM2010)
  • Place of Presentation: Honolulu(USA)
  • Year and Date: 2010-12-17
• [Presentation] Diverse Reactions of Sterically Protected 1,3-Diphosphacyclobutane-2,4-diyls with Hydride (2010)
  • Author(s): S.Ito, J.Miura, N.Morita, M.Yoshifuji, A.J.Arduengo
  • Organizer: 2010 International Conference on Phosphorus Chemistry
  • Place of Presentation: Wroclaw(Poland)
  • Year and Date: 2010-07-13