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超長寿命・高エネルギー電荷分離状態を利用した有機光触媒反応システムの開発

Research Project

Project/Area Number 17750039
Research Category

Grant-in-Aid for Young Scientists (B)

Allocation TypeSingle-year Grants
Research Field Organic chemistry
Research InstitutionOsaka University

Principal Investigator

大久保 敬  大阪大学, 大学院工学研究科, 特別科学研究員 (00379140)

Project Period (FY) 2005 – 2006
Project Status Completed (Fiscal Year 2006)
Budget Amount *help
¥3,600,000 (Direct Cost: ¥3,600,000)
Fiscal Year 2006: ¥1,600,000 (Direct Cost: ¥1,600,000)
Fiscal Year 2005: ¥2,000,000 (Direct Cost: ¥2,000,000)
Keywords電子移動 / 光化学 / 電荷分離 / フラーレン / 光合成 / ドナー・アクセプター連結系 / レーザーフラッシュフォトリシス / パイ電子系 / フタロシアニン / エネルギー移動 / 電荷再結合
Research Abstract

ドナー・アクセプター連結系分子を用いて電荷分離状態を得るには、最初の光誘起電荷分離過程が逆電子移動による電荷再結合過程よりもはるかに速く起こる必要がある。そのためには電子移動の再配列エネルギー(λ)を小さくすれば良い。その場合λが小さくなると、電荷再結合過程の速度は電荷分離過程の速度よりもはるかに遅くなることが可能となる。そこで、2次元のパイ電子系を有するフラーレンの電子移動特性について検討を行った。その中でも、再配列エネルギーが最も小さいと言われているフラーレンは最近特に注目を集めている。本年度では、トリニトロフルオレノンとフラーレンを連結させた分子に金属イオンを添加することにより、フラーレンを分子内電子移動酸化することによって長寿命電荷分離状態を生成させることについて検討を行った。
トリニトロフルオレノン-フラーレン連結分子(TNF-C_<60>)の脱酸素ベンゾニトリル溶液のサイクリックボルタモグラムでは4つの可逆な還元波と1つの酸化波が観測された。参照化合物のCVとの比較によりTNF(-0.40V vs SCE), TNF/C_<60>(-0.70V), C_<60>(-1.11V)の順で還元が起こっていることがわかった。一方、一電子酸化はC_<60>上で起こっていることがわかった。TNF-C_<60>の一電子酸化電位と一電子還元電位の差から電荷分離状態のエネルギーを1.89eVと決定した。次にTNF-C_<60>の脱酸素ベンゾニトリル溶液に530nmのレーザーフラッシュ照射を行い選択的にフラーレン部位を光励起すると、2マイクロ秒後に720nmに吸収極大を有する3重項励起状態フラーレン(^3C_<60>^*)に特徴的な過渡吸収帯が観測された。C_<60>の一重項励起状態のエネルギーは1.75eVであり、、この場合電子移動の自由エネルギー変化が正となるため電子移動は進行せず、項間交差によって^3C_<60>^*が生成したものと考えられる。この系にスカンジウムイオンを添加し同様な測定を行うと、C_<60>部位からTNF部位への電子移動反応が進行し、過渡吸収スペクトルで電荷分離状態が観測された。電荷分離寿命は室温で23ミリ秒と非常に長いことが分かった。この電荷分離状態は、溶液中における電荷分離寿命の世界最長記録(2007年2月現在)である。

Report

(2 results)
  • 2006 Annual Research Report
  • 2005 Annual Research Report
  • Research Products

    (53 results)

All 2007 2006 2005

All Journal Article (53 results)

  • [Journal Article] An Extremely Long-Lived Charge-Separated State of Zinc Tetraphenylporphyrin Coordinated with Pyridylnaphthalenediimide2007

    • Author(s)
      Kei Ohkubo at al
    • Journal Title

      Journal of Porphyrins Phthalocyanines 11(印刷中)

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Efficient Photocatalytic Hydrogen Evolution without an Electron Mediator Using a Simple Electron Donor-Acceptor Dyad2007

    • Author(s)
      Kei Ohkubo at al
    • Journal Title

      Physical Chemistry Chemical Physics (印刷中)

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Fullerene Acting as an Electron Donor in a Donor-Acceptor Dyad to Attain the Long-Lived Charge-Separated State by Complexation with Scandium Ion2007

    • Author(s)
      Kei Ohkubo at al
    • Journal Title

      Chemical Communications

      Pages: 589-591

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Modulation of Characteristics of a Ruthenium-Coordinated Flavin Analog Showing an Unprecedented Coordination Mode2007

    • Author(s)
      Kei Ohkubo at al
    • Journal Title

      Angewandte Chemie, International Edition 46

      Pages: 905-908

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Photocatalytic Formation of Dimethyllepidopterene from 9,10-Dimethylanthracene via Electron-Transfer Oxidation2007

    • Author(s)
      Kei Ohkubo at al
    • Journal Title

      Organic Letters 8

      Pages: 6079-6082

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Scandium Ion-Accelerated Scavenging Reaction of Cumylperoxyl Radical by a Cyclic Nitroxyl Radical via Electron Transfer2007

    • Author(s)
      Kei Ohkubo at al
    • Journal Title

      Chemistry Letters

      Pages: 378-379

    • NAID

      10018829397

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Model Studies of 6,7-Indolequinone Cofactors of Quinohemoprotein Amine Dehydrogenases2007

    • Author(s)
      Kei Ohkubo at al
    • Journal Title

      Journal of Organic Chemistry (印刷中)

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Electron-Transfer Oxidation Properties of Unsaturated Fatty Acids and Mechanistic Insight into Lipoxygenases2006

    • Author(s)
      Kei Ohkubo at al
    • Journal Title

      The Journal of Physical Chemistry A 110

      Pages: 1718-1725

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Hydrogen Abstraction from Neurotransmitters by Active Oxygen Species Facilitated by Intramolecular Hydrogen Bonding in the Radical Intermediates2006

    • Author(s)
      Kei Ohkubo at al
    • Journal Title

      Organic & Biomolecular Chemistry 4

      Pages: 999-1001

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Photoinduced Electron-Transfer Dynamics and Long-lived CS States of Donor-Acceptor Linked Dyads and a Triad Containing a Gold Porphyrin in Nonpolar Solvents2006

    • Author(s)
      Kei Ohkubo at al
    • Journal Title

      Chemical Physics 326

      Pages: 3-14

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Photocatalytic Oxygenation of Olefins with Oxygen. Isolation of 1,2-Dioxetane and the Photocatalytic O-O Bond Cleavage2006

    • Author(s)
      Kei Ohkubo at al
    • Journal Title

      Catalysis Today 117

      Pages: 356-361

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Photocatalytic Oxygenation of Pivalic Acid with Molecular Oxygen via Photoinduced Electron Transfer Using 10-Methylacridinium Ions2006

    • Author(s)
      Kei Ohkubo at al
    • Journal Title

      The Journal of Physical Chemistry A 110

      Pages: 3860-3867

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Additivity Rule Holds in Hydrogen-Transfer Reactivity of Unsaturated Fatty Acids with a Peroxyl Radical : Mechanistic Insight into Lipoxygenase2006

    • Author(s)
      Kei Ohkubo at al
    • Journal Title

      Chemical Communications

      Pages: 979-981

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Structual Basis for DNA-Cleaving Activity of Resveratrol in the Presence of Cu(II)2006

    • Author(s)
      Kei Ohkubo at al
    • Journal Title

      Bioorganic Medical Chemistry 14

      Pages: 1437-1443

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Organotin Perfluorooctanesulfonates as Air-Stable Lewis Acid Catalysts : Synthesis, Characterization, and Catalysis2006

    • Author(s)
      Kei Ohkubo at al
    • Journal Title

      Chemistry -A European Journal 12

      Pages: 1642-1647

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Solvent-Free Selective Photocatalytic Oxidation of Benzyl Alcohol to Benzaldehyde by Molecular Oxygen using 9-Phenyl-10-methylacridinium2006

    • Author(s)
      Kei Ohkubo at al
    • Journal Title

      Chemical Communications

      Pages: 2018-2020

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Direct Detection of Nucleotide Radical Cations Produced by Electron-Transfer Oxidation of DNA Bases with Electron-Transfer State of 9-Mesityl-10-methylacridinium Ion and Resulting Efficient DNA Cleavage without Oxygen2006

    • Author(s)
      Kei Ohkubo at al
    • Journal Title

      Chemical Communications

      Pages: 2504-2506

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Photoinduced Electron-Transfer Dynamics and Long-lived CS States of Donor-Acceptor Linked Dyads and a Triad Containing a Gold Porphyrin in Nonpolar Solvents2006

    • Author(s)
      Kei Ohkubo at al
    • Journal Title

      Bulletin Chemical Society of Japan 79

      Pages: 1489-1500

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Host-Guest Complexation of Endohedral Metallofullerene with Azacrown Ether and Its Application2006

    • Author(s)
      Kei Ohkubo at al
    • Journal Title

      Journal of the American Chemical Society 12

      Pages: 167-176

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Formation of a Charge-Separated State of a Fullerene-Trinitrofluorenone Dyad by Complexation with Scandium Ion2006

    • Author(s)
      Kei Ohkubo at al
    • Journal Title

      ECS Transaction 12

      Pages: 15-25

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Porphyrin Nanochannels toward Photofunctional Materials2006

    • Author(s)
      Kei Ohkubo at al
    • Journal Title

      Journal of Porphyrins Phthalocyanines 10

      Pages: 322-322

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Phthalocyanine-Perylene Dyad-Based Photovoltaic Cell Preparation2006

    • Author(s)
      Kei Ohkubo at al
    • Journal Title

      Journal of Porphyrins Phthalocyanines 10

      Pages: 502-502

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Photoinduced Electron Transfer in Porphyrin-Based Covalent and Non-Covalent Triads2006

    • Author(s)
      Kei Ohkubo at al
    • Journal Title

      Journal of Porphyrins Phthalocyanines 10

      Pages: 590-590

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Photochemical Properties of Porphyrins Nanochannels to Exhibit Photofunctionality2006

    • Author(s)
      Kei Ohkubo at al
    • Journal Title

      Journal of Porphyrins Phthalocyanines 10

      Pages: 785-785

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Photoinduced Charge Separation of Zinc Chlorin-Fullerene Dyads Directly Linked at Different Positions2006

    • Author(s)
      Kei Ohkubo at al
    • Journal Title

      Journal of Porphyrins Phthalocyanines 10

      Pages: 802-802

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Photodynamics in Various Complexes between Acridinium Ion and Free-Base, Monozinc and Zinc Bisporphyrins2006

    • Author(s)
      Kei Ohkubo at al
    • Journal Title

      Journal of Porphyrins Phthalocyanines 10

      Pages: 892-892

    • Related Report
      2006 Annual Research Report
  • [Journal Article] DNA Cleavage by UVA Irradiation of NADH with Dioxygen via Radical Chain Processes2006

    • Author(s)
      Kei Ohkubo at al
    • Journal Title

      The Journal of Physical Chemistry A 110

      Pages: 11214-11218

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Persistent Electron-Transfer State of a π-Complex of Acridinium Ion Inserted between Porphyrin Rings of Cofacial Bisporphyrins2006

    • Author(s)
      Kei Ohkubo at al
    • Journal Title

      Journal of the American Chemical Society 128

      Pages: 11613-11616

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Reductive DNA Cleavage Induced by UVA Photoirradiation of NADH without Oxygen2006

    • Author(s)
      Kei Ohkubo at al
    • Journal Title

      Journal of the American Chemical Society 128

      Pages: 12372-12373

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Activation of Electron-Transfer Reduction of Oxygen by Hydrogen Bond Formation of Superoxide Anion with Ammonium Ion2006

    • Author(s)
      Kei Ohkubo at al
    • Journal Title

      The Journal of Physical Chemistry A 110

      Pages: 11613-11616

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Viologen-Modified Platinum Clusters Acting as an Efficient Catalyst in Photocatalytic Hydrogen Evolution2006

    • Author(s)
      Kei Ohkubo at al
    • Journal Title

      The Journal of Physical Chemistry B 110

      Pages: 24047-24053

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Spin-Site Exchange System Constructed from Endohedral Metallofullerenes and Organic Donors2006

    • Author(s)
      Kei Ohkubo at al
    • Journal Title

      Journal of the American Chemical Society 128

      Pages: 14418-14419

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Electron-Transfer Oxidation Properties of Unsaturated Fatty Acids and Mechanistic Insight into Lipoxygenases2006

    • Author(s)
      Kei Ohkubo et al.
    • Journal Title

      The Journal of Physical Chemistry A 109(印刷中)

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Hydrogen Abstraction from Neurotransmitters by Active Oxygen Specie Facilitated by Intramolecular Hydrogen Bonding in the Radical Intermediates2006

    • Author(s)
      Kei Ohkubo et al.
    • Journal Title

      Organic & Biomolecular Chemistry 4(印刷中)

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Photoinduced Electron-Transfer Dynamics and Long-lived CS States of Donor-Acceptor Linked Dyads and a Triad Containing a Gold Porphyrin in Nonpolar Solvents2006

    • Author(s)
      Kei Ohkubo et al.
    • Journal Title

      Chemical Physics (印刷中)

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Photocatalytic Oxygenation of Olefins with Oxygen. Isolation of 1,2-Dioxetane and the Photocatalytic O-O Bond Cleavage2006

    • Author(s)
      Kei Ohkubo et al.
    • Journal Title

      Catalysis Today (印刷中)

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Photocatalytic Oxygenation of Pivalic Acid with Molecular Oxygen via Photoinduced Electron Transfer Using 10-Methylacridinium Ions2006

    • Author(s)
      Kei Ohkubo et al.
    • Journal Title

      The Journal of Physical Chemistry A (印刷中)

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Additivity Rule Holds in Hydrogen-Transfer Reactivity of Unsaturated Fatty Acids with a Peroxyl Radical : Mechanistic Insight into Lipoxygenase2006

    • Author(s)
      Kei Ohkubo et al.
    • Journal Title

      Chemical Communications (印刷中)

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Structual Basis for DNA-Cleaving Activity of Resveratrol in the Presence of Cu(II)2006

    • Author(s)
      Kei Ohkubo et al.
    • Journal Title

      Bioorganic Medical Chemistry (印刷中)

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Electron-Transfer Oxidation of Coenzyme B12 Model Compounds and Facile Cleavage of the Cobalt(IV)-Carbon Bond via Charge-Transfer Complexes with Bases. A Negative Temperature Dependence of the Rates2005

    • Author(s)
      Kei Ohkubo et al.
    • Journal Title

      The Journal of Physical Chemistry A 109・6

      Pages: 1105-1113

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Electron-transfer mechanism in radical-scavenging reactions by a vitamin E model in a protic medium2005

    • Author(s)
      Kei Ohkubo et al.
    • Journal Title

      Organic & Biomolecular Chemistry 3

      Pages: 626-629

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Electron-Transfer Oxidation Properties of DNA Bases and DNA Oligomers2005

    • Author(s)
      Kei Ohkubo et al.
    • Journal Title

      The Journal of Physical Chemistry A 109・15

      Pages: 3285-3294

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Direct ESR Detection of Pentadienyl Radicals and Peroxyl Radicals in Lipid Peroxidation : Mechanistic Insight into Regioselective Oxygenation in Lipoxygenases2005

    • Author(s)
      Kei Ohkubo et al.
    • Journal Title

      Journal of American Chemical Society 127・18

      Pages: 6605-6609

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Effects of DNA on Driving Force Dependence of Photoinduced Electron Transfer from the Excited State of Tris(2,2-bipyridine)ruthenium(II) to Intercalators in DNA. Distinction between Intra- and Inter-DNA Pathways2005

    • Author(s)
      Kei Ohkubo et al.
    • Journal Title

      Journal of Photochemistry & Photobiology A Chemistry 175

      Pages: 79-88

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Electrochemistry of [(TMpyP)M^<II>]^<4+>(X^-)_4(X^-=Cl^- or BPh_4^-) and [(TMpyP)M^<III>Cl]^<4+>-(Cl^-)_4 in N,N-Dimethylformamide Where M Is One of 15 Different Metal Ions2005

    • Author(s)
      Kei Ohkubo et al.
    • Journal Title

      Inorganic Chemistry 44・11

      Pages: 3789-3798

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Formation of a Long-Lived Charge-Separated State of a Zinc Phthalocyanine-Perylenediimide Dyad by Complexation with Magnesium Ion2005

    • Author(s)
      Kei Ohkubo et al.
    • Journal Title

      Chemical Communications

      Pages: 3814-3815

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Misleading Effects of Impurities Derived from Extremely Long-lived Electron-transfer State of 9-Mesityl-10-methylacridinium ion2005

    • Author(s)
      Kei Ohkubo et al.
    • Journal Title

      Chemical Communications 36

      Pages: 4520-4522

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Charge Separation in a Nonfluorescent Donor-Acceptor Dyad Derived from Boron Dipyrromethene Dye, Leading to Photocurent Generation2005

    • Author(s)
      Kei Ohkubo et al.
    • Journal Title

      The Journal of Physical Chemistry B 109・32

      Pages: 15368-15375

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Intramolecular Hydrogen Bonding in Bisphenol Developing Agents for Photothermographic Application2005

    • Author(s)
      Kei Ohkubo et al.
    • Journal Title

      Journal of Imaging Science Technology 49・4

      Pages: 381-388

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Hydroxyl Radical Generation via Photoreduction of a Simple Pyridine N-oxide by an NADH Analogue2005

    • Author(s)
      Kei Ohkubo et al.
    • Journal Title

      Organic & Biomolecular Chemistry 3

      Pages: 3263-3265

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Efficient Photocatalytic Oxygenation of Aromatic Alkene to 1,2-Dioxetane with Oxygen via Electron Transfer2005

    • Author(s)
      Kei Ohkubo et al.
    • Journal Title

      Organic Letters 7・19

      Pages: 4265-4268

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Selective Oxygenation of 4,4'-Dimethylbiphenyl with Molecular Oxygen, Catalyzed by 9-Phenyl-10-Methylacridinium Ion Via Photoinduced Electron Transfer2005

    • Author(s)
      Kei Ohkubo et al.
    • Journal Title

      The Journal of Physical Chemistry A 109・44

      Pages: 10168-10175

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Anti-chagasic Activity of Komaroviquinone is due to Generation of Reactive Oxygen Species Catalyzed by Trypanosoma cruzi Old Yellow Enzyme2005

    • Author(s)
      Kei Ohkubo et al.
    • Journal Title

      Antimicrobial Agents and Chemotherapy 49・12

      Pages: 5123-5126

    • Related Report
      2005 Annual Research Report

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Published: 2005-04-01   Modified: 2016-04-21  

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