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Approach to Biradical Chemistry utilizing Photoindeced Electron Transfer

Research Project

Project/Area Number 12440173
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Research Field Organic chemistry
Research InstitutionTohoku University

Principal Investigator

MIYASHI Tsutomu  Tohoku University,Graduate School of Science Professor, 大学院・理学研究科, 教授 (20004442)

Co-Investigator(Kenkyū-buntansha) IKEDA Hiroshi  Tohoku University,Graduate School of Science Assistant of Professor, 大学院・理学研究科, 助手 (30211717)
Project Period (FY) 2000 – 2002
Project Status Completed (Fiscal Year 2002)
Budget Amount *help
¥13,800,000 (Direct Cost: ¥13,800,000)
Fiscal Year 2002: ¥3,000,000 (Direct Cost: ¥3,000,000)
Fiscal Year 2001: ¥3,400,000 (Direct Cost: ¥3,400,000)
Fiscal Year 2000: ¥7,400,000 (Direct Cost: ¥7,400,000)
KeywordsPhotochemistry / Biradical / Cation Radical / Electron Transfer / Trimethylenemethane / Tetramethyleneethane / Back Electron Transfer / Stereochemistry / テトラメチレンメタン / レーザー
Research Abstract

We studied the new generation and characterization of various biradicals generated in the photoinduced electron transfer reactions [(1)-(7) except for (6)] and a related direct irradiation reaction [(6)]. In the former, the keys step is a facile back electron transfer in a radical ion pair, which converts quantitatively the reactive radical cation intermediates to the corresponding diradicals.
As results, we have found novel cation radicals and biradicals which undergo unprecedented reactions, and gained valuable insights into steric and electronic structures of controversial biradicals. The studies is still now in progress and thus, next year, we will apply a grant-in-aid to the Ministry of Education, Culture, Sports, Science, and Technology.
(1) Photoinduced Electron Transfer Reactions of 2,2-Diaryl-1-methylenecyclopropane.
(2) Photoinduced Electron Transfer Reactions of 5,5-Dimethyl-2,3-bis(α-styryl)-1,3-cyclobutadiene.
(3) Photoinduced Electron Transfer Reactions of cis-and trans-2-Anisyl-3-methyl-1-methylenecyclopropane and cis-and trans-2-Anisyl-1-ethylidenecyclopropane.
(4) Photoinduced Electron Transfer Reactions of 7-(Dianisylmethylene)-2,3-diazabicyclo[2.2.1]hept-2-ene.
(5) Photoinduced Electron Transfer Reactions of 3,3-Dimethy1-4-methylene-2,2-bis(4-methoxyphenyl)cyclobutanone and 4-Isopropilidene-2-bis(4-methoxyphenyl)cyclobutanone.
(6) Direct Irradiation reaction of 7-(Diarylmethylene)-2,3-diazabicyclo[2.2.1]hept-2-ene.
(7) Photoinduced Electron Transfer Reactions of 1,2-Bis(α-styryl)benzenes and 3,4-bis(α-styryl)furans.

Report

(4 results)
  • 2002 Annual Research Report   Final Research Report Summary
  • 2001 Annual Research Report
  • 2000 Annual Research Report
  • Research Products

    (27 results)

All Other

All Publications (27 results)

  • [Publications] T.N.Inada, K.Kikuchi, Y.Takahashi, H.Ikeda, T.Miyashi: "A Comparative Study on Electron-Transfer Fluorescence Quenching by Aliphatic and Aromatic Amines"J.Photochem.Photobiol.A.Chem.. 137. 93-97 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] N.Iki, C.Kabuto, T.Fukushima, H.Kumagai, H.Takeya, S.Miyanari, T.Miyashi, S.Miyano: "Synthesis of p-tert-butylthiacalix[4]arene and Its Inclusion Property"Tetrahedron. 56. 1437-1443 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] H.Ikeda, N.Aburakawa, F.Tanaka, T.Fukushima, T.Miyashi: "Photosensitized Electron-Transfer Reactions of 1-Isopropylidene-2-methylene-3,3-diphenylcyclobutane-[4+4] Cycloaddition and Cyclodimerization Initiated by a Buta-1,3-diene Radical Cation Functionality"Eur.J.Org.Chem.. 3445-3452 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] H.Ikeda, Y.Hoshi, T.Miyashi: "1,3-Bis(4-methoxyphenyl)cyclohexane-1,3-diyl Cation Radical : Change of Reactivity Depending upon One-electron Oxidation Conditions"Tetrahadron Lett.. 42. 8485-8488 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] T.Suzuki, S.Miyanari, Y.Tsubata, T.Fukushima, T.Miyashi, Y.Yamashita, K.Imaeda, T.Ishida, T.Nogami: "Single-Component Organic Semiconductors Based on Novel Radicals that Exhibit Electrochemical Amphotericity : Preparation, Crystal Structures, and Solid-State Properties of N, N'-Dicyanopyrazinonaphthoquinodiiminides Substituted with an N-Alkylpyridinium Unit"J.Org.Chem.. 66. 216-224 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] T.Suzuki, T.Tsuji, T.Okubo, A.Okada, Y.Obana, T.fukushima, T.Miyashi, Y.Yamashita: "Preparation, Structure, and Amphoteric Redox Properties of p-Phenylenediamine-Type Dyes Fused with a Chalcogenadiazole Unit"J.Org.Chem.. 66. 8954-8960 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] T.Inada, K.Kikuchi, Y.Takahashi, H.Ikeda, T.Miyashi: "Electron-Transfer (ET) Fluorescence Quenching in Benzonitrile. Evidence of an Intermolecular ET with ΔG<-0.5eV being a Diffusion-Controlled Process"J.Phys.Chem.A. 106. 4345-4349 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] H.Ikeda, K.Akiyama, Y.Takahashi, T.Nakamura, S.Ishizaki, Y.Shiratori, H.Ohaku, J.L.Goodman, A.Houmam, D.D.M.Wayner, S.Tero-Kubota, T.Miyashi: "Spectroscopic and Calorimetric Studies on the Mechanism of Methylenecyclopropane Rearrangements Triggered by Photoinduced Electron transfer"J.Am.Chem.Soc.. 125(In press). (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] 池田 浩: "ゼオライトの超分子立体効果と高い酸化力を利用した反応性中間体"光化学(光化学協会). 31号. 3 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] 池田 浩, 宮仕 勉: "(学会における光触媒研究の最先端)有機物ラジカルイオンの反応性および機構の検討と光触媒上での活性種の特定に関する研究課題"会報 光触媒(光機能材料研究会). 7号. 4 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] 池田 浩, 宮仕 勉: "ジフェニル置換したメチレンシクロプロパンの溶液中およびゼオライト界面における電子移動反応"会報 光触媒(光機能材料研究会). 9号. 2 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] T.N.Inada, K.Kikuchi, Y.Takahashi, H.Ikeda, T.Miyashi: "A Comparative Study on Electron-Transfer Fluorescence Quenching by Aliphatic and Aromatic Amines"J. Photochem. Photobiol. A. Chem.. 137. 93-97 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] N.Iki, C.Kabuto, T.Fukushima, H.Kumagai, H.Takeya, S.Miyanari, T.Miyashi and S.Miyano: "Synthesis of p-tert-butylthiacalix[4]arene and Its Inclusion Property"Tetrahedron. 56. 1437-1443 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] H.Ikeda, N.Aburakawa, F.Tanaka, T.Fukushima and T.Miyashi: "Photosensitized Electron-Transfer Reactions of 1-Isopropylidene-2-methylene-3,3-diphenylcyclobutane - [4+4]Cycloaddition and Cyclodimerization Initiated by a Buta-1,3-diene Radical Cation Functionality"Eur.J.Org.Chem.. 3445-3452 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] H.Ikeda, Y.Hoshi and T.Miyashi: "1,3-Bis(4-methoxyphenyl)cyclohexane-1,3-diyl Cation Radical: Change of Reactivity Depending upon One-electron Oxidation Conditions"Tetrahadron Lett.. 42. 8485-8488 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] T.Suzuki, S.Miyanari, Y.Tsubata, T.Fukushima, T.Miyashi, Y.Yamashita, K.Imaeda, T.Ishida, and T.Nogami: "Single-Component Organic Semiconductors Based on Novel Radicals that Exhibit Electrochemical Amphotericity: Preparation, Crystal Structures, and Solid-State Properties of N,N'-Dicyanopyrazinonaphthoquinodiiminides Substituted with an N-Alkylpyridinium Unit"J.Org.Chem.. 66. 216-224 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] T.Suzuki, T.Tsuji, T.Okubo, A.Okada, Y.Obana, T.Fukushima, T.Miyashi and Y.Yamashita: "Preparation, Structure, and Amphoteric Redox Properties of p-Phenylenediamine-Type Dyes Fused with a Chalcogenadiazole Unit."J.Org.Chem.. 66. 8954-8960 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] T.Inada, K.Kikuchi, Y.Takahashi, H.Ikeda, T.Miyashi: "Electron-Transfer (ET) Fluorescence Quenching in Benzonitrile. Evidence of an Intermolecular ET with DG 0x(3C)-0.5 eV being a Diffusion-Controlled Process"J.Phys.Chem.A. 106. 4345-4349 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] H.Ikeda, K.Akiyama, Y.Takahashi, T.Nakamura, S.Ishizaki, Y.Shiratori, H.Ohaku, J.L.Goodman, A.Houmam, D.D.M.Wayner, S.Tero-Kubota and T.Miyashi: "Spectroscopic and Calorimetric Studies on the Mechanism of Methylenecyclopropane Rearrangements Triggered by Photoinduced Electron transfer"J.Am.Chem.Soc.. In press. (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] T.Inada, K.Kikuchi, Y.Takahashi, H.Ikeda, T.Miyashi: "Electron-Transfer (ET) Fluorescence Quenching in Benzonitrile. Evidence of an Intermolecular ET with ΔG<-0.5eV being a Diffiusion-Controlled Process"J. Phys. Chem. A. 106. 4345-4349 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] H.Ikeda, T.Miyashi, et al.(他10人): "Spectroscopic and Calorimetric Studies on the Mechanism of Methylenecyclopropane Rearrangements Triggered by Photoinduced Electron transfer"J. Am. Chem. Soc.. 25(In press). (2003)

    • Related Report
      2002 Annual Research Report
  • [Publications] 池田 浩, 宮仕 勉: "会報 光触媒7号(学会における光触媒研究の最先端) 有機物ラジカルイオンの反応性および機構の検討と光触媒上での活性種の特定に関する研究"光機能材料研究会. 4 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] 池田 浩, 宮仕 勉 他: "会報 光触媒9号 ジフェニル置換したメチレンシクロプロパンの溶液中およびゼオライト界面における電子移動反応"光機能材料研究会. 2 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] H.Ikeda, N.Aburakawa, F.Tanaka, T.Fukushima, T.Miyashi.: "Photosensitized Electron-Transfer Reactions of 1-Isopropylidene-2-methylene-3,3-diphenylcyclobutane-[4+4]Cycloaddition and Cyclodimerization Initiated by a Buta-1,3-diene Radical Cation Functionality"Eur. J. Org. Chem.. 3445-3452 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] H.Ikeda, Y.Hoshi, T.Miyashi.: "1,3-Bis(4-methoxyphenyl)cyclohexane-1,3-diyl Cation Radical : Change of Reactivity Depending upon One-electron Oxidation Conditions"Tetrahadron Lett.. 42. 8485-8488 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] T.N.Inada,K.Kikuchi,Y.Takahashi,H.Ikeda and T.Miyashi: "A comparative study on electron-transfer fluorescence quenching by aliphatic and aromatic amines"J.Photochem.Photobiol.A.Chem.. 137・?. 93-97 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] 池田浩: "光化学"ゼオライトの超分子立体効果と高い酸化力を利用した反応性中間体の化学Remarkable Persistence and Unique Reactivity of Reactive Intermediates in Zeolites Induced by Supermolecular Steric Effects and High Oxidizing Power. 3 (2000)

    • Related Report
      2000 Annual Research Report

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Published: 2000-04-01   Modified: 2016-04-21  

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