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数珠玉状および網目状フラーレン連結分子の光化学反応による生成

Research Project

Project/Area Number 11875187
Research Category

Grant-in-Aid for Exploratory Research

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

Principal Investigator

真嶋 哲朗  大阪大学, 産業科学研究所, 教授 (00165698)

Co-Investigator(Kenkyū-buntansha) 佐治 幸子 (藤乗 幸子)  大阪大学, 産業科学研究所, 助手 (50197844)
一ノ瀬 暢之  大阪大学, 産業科学研究所, 助手 (00232405)
石田 昭人  大阪大学, 産業科学研究所, 助手 (20184525)
川井 清彦  大阪大学, 産業科学研究所, 助手 (50314422)
Project Period (FY) 1999 – 2000
Project Status Completed (Fiscal Year 2000)
Budget Amount *help
¥2,300,000 (Direct Cost: ¥2,300,000)
Fiscal Year 2000: ¥500,000 (Direct Cost: ¥500,000)
Fiscal Year 1999: ¥1,800,000 (Direct Cost: ¥1,800,000)
Keywordsフラーレン / 光化学反応 / ビラジカル / フラーレン連結分子 / フラシュホトリシス / レーザー励起 / フラッシュホトリシス
Research Abstract

本研究では、有機分子の光化学反応によってビラジカルを発生させ、「ラジカルスポンジ」としてのC_<60>フラーレンに付加反応することを利用して、数珠玉状および網目状フラーレン連結分子の生成について検討した。有機光化学反応によるビラジカル発生法として、種々のシクロアルカンの環のC-C結合開裂、シクロアルカノンのアシル基のα開裂によって、アルカンのメチレン鎖を変化させることによる1,n-ビラジカルの発生、カルボニル基の分子内γ水素引き抜きによる1,4-ビラジカルの発生を、溶液中のレーザーフラッシュホトリシス法(励起レーザーとして主にXeClエキシマーレーザー308nm光を使用)によるビラジカルの過渡吸収測定から検討した。この結果、様々な原料を使用した光化学反応によって様々なビラジカルを発生させることができ、原料の有機分子の吸収にあった波長の高強度のレーザー光を照射することによって光化学反応を効率的に起こし、高密度・高濃度のビラジカルを発生させることが可能であることがわかった。次に、溶液中にC_<60>フラーレンを共存させておき、前述のXeClエキシマーレーザー励起による有機光化学反応によってビラジカルを発生させ、ビラジカルとC_<60>フラーレンとの付加反応を検討した。これら混合系では、ビラジカルの過渡吸収がC_<60>フラーレン基底状態の吸収と重なっているため、ビラジカルの過渡吸収測定は困難であった。また、C_<60>フラーレン自身もXeClエキシマーレーザー照射によって励起される。しかし、両者の濃度調整によって有機化合物の光化学反応を優先的に起こし、ビラジカルを発生させることができる場合を見い出した。実際に生成した炭素成分の質量測定によれば、数珠玉状および網目状フラーレン連結分子が生成している可能性が示唆された。

Report

(2 results)
  • 2000 Annual Research Report
  • 1999 Annual Research Report

Research Products

(29 results)

All Other

All Publications (29 results)

  • [Publications] Tetsuro Majima: "Decomposition of cyclopentadienyltricarbonylmanganese in highly vibrational excited states"J.Organomet.Chem.. 574・1. 155-162 (1999)

    • Related Report
      2000 Annual Research Report
  • [Publications] Kakuzo Isagawa: "Preparation of (E)-and(Z)-1,3,4,6-Tetrapheny-3-hexen-1,5-diyaes from 1,1-Dibromo-2,3-diphenylcyclopropanes"Tetrahedron Lett.. 40. 9051-9053 (1999)

    • Related Report
      2000 Annual Research Report
  • [Publications] Akito Ishida: "Surface Plasmon Excitation of Porphyrin Self-assembly Monolayers on a Gold Surface"Nanotechnology. 10. 1-7 (1999)

    • Related Report
      2000 Annual Research Report
  • [Publications] Akito Ishida: "Surface Plasmon Enhanced Fluorescence Spectroscopy towards Observation of Molecular Exchange in a Self-Assembly Monolayer"Chem.Commun.. 1999. 1299-1300 (1999)

    • Related Report
      2000 Annual Research Report
  • [Publications] Akito Ishida: "Photocurrent Generation of a Porphyrin Self-Asembly Monolayer on a Gold Film Electron by Surface Plasmon Excitation using Near-IRLight"Chem Phys.Lett.. 322. 242-246 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] Akito Ishida: "Surface Plasmon Enhanced Fluorescence Measurement on Flat and Constructed Gold Surfaces"Analyst. 125. 535-540 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] Mitsunobu Nakamura: "Effects of Methylene Chains on Photoreactions of Diphenylalkanediones and Phenylalkenenones"J.Chem.Soc.Perkin 1.. 2000・3. 415-420 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] Mitsunobu Nakamura: "9,10-Dicyanoanthracene-Photosensitized Elimination of 1,1'-Binaphthalene from Dinaphthyl Methylphosphonate and Trinaphthyl Phosphate through the Termolecular Interaction in the Singlet Excited State"Bull.Chem.Soc.Jpn.. 72. 2103-2109 (1999)

    • Related Report
      2000 Annual Research Report
  • [Publications] Mitsunobu Nakamura: "Mechanistic Study of Photoinduced Electron-Transfer Reaction of Parasubstituted Triphenylphosphines Sensitised by 9,10-Dicyanoanthracene"J.Chem.Soc.Perkin 2.. 2000. 1447-1452 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] Nobuyuki Ichinose: "Transient Absorption and Fluorescence Measurements of Free Radical Cation and Radical Ion Pair during Pulse Radiolysis of 1,3,5-Trimethoxybenzene in Chlorinated Solvents"Chem Phys.Lett.. 322. 15-20 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] Nobuyuki Ichinose: "Energy Transfer Quenching of a Fluorescent Excited Radical Cation by Counter Radical Anion : Dissipation of Radical Ions Generated by Photoinduced Electron Transfer"Chem Phys.Lett.. 326. 293-298 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] Nobuyuki Ichinose: "Fluorescence Measurement of 3,5-Dimethoxyphenol Radical Cation Generated by Pulse Radiolysis in 1,2-Dichloroethane"Chem.Lett.2000. 1126-1127 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] Nobuyuki Ichinose: "Intramolecular Dimer Radical Anion of 1,1-Bis(4-cyanophenyl) and 1,1-Bis(4-methoxycarbonylphenyl) methands"Chem.Phys.Lett.. 330. 97-102 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] K.Kawai: "Selective Enhancement of One-Electron Oxidation of Guanine by Base-Pairing with Cytosine"Angew.Chem.Int.Ed.Eng.as a Common. 39. 4331-4333 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] Kyoko Sugita: "^<18>O-selective Infrared Multiple Photon Decomposition of Natural and ^<18>O-Enriched Diisopropyl Ethers"J.Phys.Chem.A. 103・21. 4144-4149 (1999)

    • Related Report
      2000 Annual Research Report
  • [Publications] Kyoko Sugita: "^<13>C-selective Infrared Multiple Photon Decomposition of β-Propiolactone, β-Butyrolactone, and Diketene with a CO_2 TEA Laser"J.Phys.Chem.A. 104. 2587-2590 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] J.-m.Park: "The Fast Photochemical[2+2]Cycloaddition and Reverse Reaction of Styrylpyrazine Amphiphile in Aqueous Dispersion"Chem Lett.1999. 1309 (1999)

    • Related Report
      2000 Annual Research Report
  • [Publications] J.-m.Park: "Remarkably Slow Aggregation of a Styrylpyrazine Amphiphile in Aqueous Dispersion"Chem.Lett.2000. 182-183 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] 川井清彦: "分子スケールの光論理ゲートの集積"光化学. 30・2. 142-143 (1999)

    • Related Report
      2000 Annual Research Report
  • [Publications] 一ノ瀬暢之: "過度発光測定法によるラジカルカチオンの動的挙動"光化学. 31・1. 2-9 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] N.Ichinose: "Fluorescent Radical Cation in Solution as a probe for Ion Pair Dynamics"The Spectrum. 13. 14-19 (2001)

    • Related Report
      2000 Annual Research Report
  • [Publications] 手老省三: "フリーラジカル-生命・環境から先端技術にわたる役割"米田出版. 196 (1999)

    • Related Report
      2000 Annual Research Report
  • [Publications] Tetsuro Majima: "Decomposition of cyclopentadienyl tricarbonylmanganese in highly vibrational excited states"J. Organomet: Chem. 574・1. 155-162 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] Kakuzo Isagawa: "Preparation of (E)-and (Z)-1, 3, 4, 6-Tetraphenyl-3-hexen-1, 5-diynes from 1, 1-Dibromo-2, 3-diphenylcyclopropanes"Tetrahedron Lett.. 40. 9051-9053 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] Akito Ishida: "Surface Plasmon Excitation of Porphyrin Self-assembly Monolayers on a Gold Surface"Nanotechnology. 10. 308-314 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] Akito Ishida: "Surface Plasmon Enhanced Fluorescence Spectroscopy towards Observation of Molecular Exchange in a Self-Assembly Monolayer"Chem. Commun.. 1999. 1299-1300 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] Mitsunobu Nakamura: "Effects of Methylene Chains on Photoreactions of Diphenylalkanediones and Pnenylalkenenones"J. Chem. Soc. Perkin 1. 2000・3. 415-420 (2000)

    • Related Report
      1999 Annual Research Report
  • [Publications] Nobuyuki Ichinose: "Transient Absorption and Fluorescence Measurements of Free Radical Cation and Radical Ion Pair during pulse Radiolysis of 1, 3, 5-Trimethoxybenzene in Chlorinated Solvents"Chem. Phys. Lett.. (印刷中). (2000)

    • Related Report
      1999 Annual Research Report
  • [Publications] 手老省三: "フリーラジカル ―生命・環境から先端技術にわたる役割―"米田出版. 196 (1999)

    • Related Report
      1999 Annual Research Report

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Published: 1999-03-31   Modified: 2016-11-11  

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