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フラーレン誘導体の光電子移動酸化反応

Research Project

Project/Area Number 13750760
Research Category

Grant-in-Aid for Young Scientists (B)

Allocation TypeSingle-year Grants
Research Field 工業物理化学
Research InstitutionOsaka University

Principal Investigator

末延 知義  大阪大学, 大学院・工学研究科, 助手 (90271030)

Project Period (FY) 2001 – 2002
Project Status Completed (Fiscal Year 2002)
Budget Amount *help
¥2,300,000 (Direct Cost: ¥2,300,000)
Fiscal Year 2002: ¥500,000 (Direct Cost: ¥500,000)
Fiscal Year 2001: ¥1,800,000 (Direct Cost: ¥1,800,000)
Keywordsフラーレン誘導体 / ラジカルカチオン / p-ベンゾキノン類 / ルイス酸 / 電子移動 / 三重項励起状態 / レーザーフラッシュフォトリシス / 触媒作用
Research Abstract

フラーレン誘導体、特に官能基の種類や付加位置の異なる異性体のラジカルカチオンの発生やそれら異性体の分光特性の比較を行った例はこれまでに無い。このラジカルカチオンはフラーレン骨格炭素ー官能基炭素結合開裂を経てフラーレン付加体カチオンとなると考えられるが、その機構や開裂様式は全く解っていない。本研究では、中性溶液条件下、種々のフラーレン誘導体を電子供与体とし、種々の電子受容体との光電子移動反応により、フラーレン誘導体の電子移動酸化を行い、得られるフラーレンカチオン種の同定を過渡的な分光学的情報とReedらの結果を比較することで行い、フラーレン誘導体のフラーレン骨格炭素ー官能基炭素、あるいはフラーレン骨格炭素ー水素結合開裂様式に関する知見を得ること目的とする。これまでに、種々のp-ベンゾキノン類と触媒である金属イオンを紅み合わせることで、p-ベンゾキノン類の電子移動酸化活性を著しく向上させることができ、フラーレン誘導体の三重項励起状態を電子移動酸化できることがわかった。フラーレン誘導体の3重項光励起状態のT-T過渡吸収スペクトル観測を励起波長可変ナノ秒レーザーフラッシュフォトリシスシステムを用いて行い、フラーレン誘導体ラジカルカチオン種の生成を近赤外波長域の特徴的な過渡吸収スペクトル変化により初めて確認することができた。本年度は、光電子移動酸化反応において生成する不安定過渡ラジカルカチオン種の低温ストップドフローESR法による同定手法を確立し、NADH類縁体ラジカルカチオンの分光学的検出に初めて成功して反応機構を明らかにした。

Report

(2 results)
  • 2002 Annual Research Report
  • 2001 Annual Research Report
  • Research Products

    (17 results)

All Other

All Publications (17 results)

  • [Publications] Tomoyoshi Suenobu et al.: "Mechanisms of Electron Transfer Oxidation of NADH Analogs and the Chemiluminescence. Detection of the Keto and Enol Radical Cations"Journal of the American Chemical Society. 125(in press). (2003)

    • Related Report
      2002 Annual Research Report
  • [Publications] Tomoyoshi Suenobu et al.: "Direct detection of radical cations of NADH analogues"Journal of the American Chemical Society. 124・49. 14538-14539 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] Tomoyoshi Suenobu et al.: "Scandium Ion-Promoted Reduction of Heterocyclic N : N Double Bond. Hydride Transfer vs Electron Transfer"Journal of the American Chemical Society. 124・42. 12566-12573 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] Tomoyoshi Suenobu et al.: "Significant Enhancement of Electron Transfer Reduction of NAD+ Analogues by Complexation with Scandium Ion and the Detection of the Radical Intermediate-Scandium Ion Complex"Journal of the American Chemical Society. 124・31. 9181-9188 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] Tomoyoshi Suenobu et al.: "Activation of electron transfer reduction of p-benzoquinone derivatives by intermolecular regioselective Hydrogen bond formation"Chemical Communications (Cambridge, United Kingdom). 17. 1984-1985 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] Tomoyoshi Suenobu et al.: "Electron transfer properties of singlet oxygen and promoting effects of scandium ion"Journal of Physical Chemistry A. 106・7. 1241-1247 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] Tomoyoshi Suenobu et al.: "Dehydrogenation vs. Oxygenation in Photosensitized Oxidation of 9-Substituted 10-Methyl-9,10-dihydroacridine in the Presence of Scandium Ion"Journal of Physical Chemistry A. 106・7. 1465-1472 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] Ogo, S.et al.: "Structural and Spectroscopic Features of a cis (Hydroxo)-Fe_<III>-(Carboxylato) Configuration as an Active Site Model for Lipoxygenases"Inorganic Chemistry. 41・21. 5513-5520 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] Tomoyoshi Suenobu et al.: "Change in Spin State and Enhancement of Redox Reactivity of Photoexcited States of Aromatic Carbonyl Compounds by Complexation with Metal Ion Salts Acting as Lewis Acids. Lewis Acid-Catalyzed Photoaddition of Benzyltrimethylsilane and Tetramethyltin via Photoinduced Electron transfer"J.Am.Chem.Soc.. 123・32. 7756-7766 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] Tomoyoshi Suenobu et al.: "Photoalkylation of 10-Alkylacridinium Ion via a Charge-Shift Type of Photoinduced Electron Transfer Controlled by Solvent Polarity"J.Am.Chem.Soc.. 123・35. 8459-8467 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] Tomoyoshi Suenobu et al.: "Metal Ion-Catalyzed Cycloaddition vs Hydride Transfer Reactions of NADH Analogues with p-Benzoquinones"J.Am.Chem.Soc.. 123・42. 10191-10199 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] Tomoyoshi Suenobu et al.: "Extremely Slow Long-Range Electron Transfer Reactions across Zeolite-Solution Interface"J.Am.Chem.Soc.. 123・45. 11331-11332 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] Tomoyoshi Suenobu et al.: "Scandium Ion-Promoted Photoinduced Electron-Transfer Oxidation of Fullerenes and Derivatives by p-Chloranil and p-Benzoquinone"J.Am.Chem.Soc.. 123・50. 12458-12465 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] Tomoyoshi Suenobu et al.: "Efficient catalysis of Rare-Earth Metal Ions in Photoinduced Electron-Transfer Oxidation of BenzylAlcohols by a Flavin Analogue"J.Phys.Chem.A. 105・46. 10501-10510 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] Tomoyoshi Suenobu et al.: "Electron Transfer Properties of Singlet Oxygen and Promoting Effects of Scandium Ion"J.Phys.Chem.A. 106・7. 1241-1247 (2002)

    • Related Report
      2001 Annual Research Report
  • [Publications] Tomoyoshi Suenobu et al.: "Dehydrogenation vs Oxygenation in Photosensitized Oxidation of 9-Substituted 10-Methyl-9, 10-Dihydroacridine in the presence of Scandium Ion"J.Phys.Chem.A. 106・7. 1465-1472 (2002)

    • Related Report
      2001 Annual Research Report
  • [Publications] Tomoyoshi Suenobu et al.: "Evaluation of Lewis Acidity of Organotin Compounds and the Catalytic Reactivity in Electron Transfer"Chem.Lett.. 978-979 (2001)

    • Related Report
      2001 Annual Research Report

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Published: 2001-04-01   Modified: 2016-04-21  

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