複核金属錯体を用いる水の光酸化触媒の開発

2003 Fiscal Year Annual Research Report

• Project/Area Number: 13440216
• Research Institution: Osaka University
• Principal Investigator: 福住 俊一 大阪大学, 大学院・工学研究科, 教授 (40144430)
• Co-Investigator(Kenkyū-buntansha): 末延 知義 大阪大学, 大学院・工学研究科, 助手 (90271030) ; 小江 誠司 大阪大学, 大学院・工学研究科, 助教授 (60290904)
• Keywords: 光合成 / 水の4電子酸化 / 複核金属錯体 / 高原子価沖粗金属ポルフィリン / 光触媒 / 地球環境 / エネルギー問題 / 電子移動

Research Abstract

自然界で行なわれている光合成では太陽エネルギーは主として水の酸化に使用される。この水の酸化により得られたエネルギーをそのまま利用すれば地球温暖化を引き起こす二酸化炭素の放出を避けることができる。しかし、水を電子源とする適当な触媒が未だ見出されていない。従って、21世紀に地球環境およびエネルギー問題の危機の根本的解決をはかるためには、水の効率的な酸化触媒を開発することが鍵となる。本研究は、複核金属錯体を用いて水の効率的な酸化触媒を開発することを目的とした。そこで、触媒にマンガンポルフィリン、酸化剤に一電子酸化剤であるルテニウム(III)トリスビピリジン錯体(Ru(bpy)_3^<3+>)を用いて電子移動反応により活性種である高原子価マンガン-オキソポルフィリン錯体を生成させ、P450モデルとなる種々のオレフィンおよびアルカンの酸素化に成功した。その際、水が酸素源になることを見いだした。また、種々のポルフィリンを触媒として用い、その触媒活性の比較を行った。さらに高効率な反応系を構築するために、マンガンポルフィリンデンドリマーを合成しマンガンポルフィリンの複核集積化を行った。その結果、マンガンポルフィリンモノマーより高い触媒活性を示した。一方、マンガンポルフィリン錯体をゼオライトに担持すると、錯体同志が近接した位置に固定され、一電子酸化剤よる水の4電子酸化による酸素発生の触媒として機能することも見出した。

Research Products

• [Publications] Fukuzumi, S. et al.: "pH-Dependent Chemoselective Synthesis of -Amino Acids. Reductive Amination of -Keto Acids with Ammonia Catalyzed by Acid-Stable Iridium Hydride Complexes in Water"Journal of the American Chemical Society. (In Press). (2004)
• [Publications] Fukuzumi, S. et al.: "A Dramatic Elongation of the Lifetime of Charge-Separated State by Complexation with Yttrium Triflate in Ferrocene-Anthraquinone Linked Dyad"Journal of the American Chemical Society. 126・1. 56-57 (2004)
• [Publications] Fukuzumi, S. et al.: "Electron-Transfer State of 9-Mesityl-10-methylacridinium Ion with a Much Longer Lifetime and Higher Energy Than That of the Natural Photosynthetic Reaction Center"Journal of the American Chemical Society. 126・6. 1600-1601 (2004)
• [Publications] Fukuzumi, S. et al.: "Highly Self-Organized Electron Transfer from an Iridium Complex to p-Benzoquinone Due to Formation of a p-Dimer Radical Anion Complex Triply Bridged by Scandium Ions"Journal of the American Chemical Society. 125・40. 12090-12091 (2003)
• [Publications] Fukuzumi, S. et al.: "Photovoltaic Properties of Self-Assembled Monolayers of Porphyrins and Porphyrin-Fullerene Dyads on ITO and Gold Surfaces"Journal of the American Chemical Society. 125・30. 9129-9139 (2003)
• [Publications] Fukuzumi, S. et al.: "Oxidation Mechanism of Phenols by Dicopper-Dioxygen(Cu2/O2) Complexes"Journal of the American Chemical Society. 125・36. 11027-11033 (2004)
• [Publications] Fukuzumi, S. et al.: "Self-Promoted Electron Transfer from Cobalt(II) Porphyrin to p-Fluoranil To Produce a Dimer Radical Anion-Cobalt(III) Porphyrin Complex"Journal of the American Chemical Society. 125・41. 12416-12417 (2003)
• [Publications] Fukuzumi, S. et al.: "Selective Oxygenation of Ring-Substituted Toluenes with Electron-Donating and Withdrawing Substituents by Molecular Oxygen via Photoinduced Electron Transfer"Journal of the American Chemical Society. 125・42. 12850-12859 (2003)
• [Publications] Fukuzumi, S. et al.: "Role of Electron-Transfer Processes in Reactions of Diarylcarbenium Ions and Related Quinone Methides with Nucleophiles"Journal of the American Chemical Society. 125・36. 10906-10912 (2003)
• [Publications] Fukuzumi, S. et al.: "Rational Design Principle for Modulating Fluorescence Properties of Fluorescein-Based Probes by Photoinduced Electron Transfer"Journal of the American Chemical Society. 125・28. 8666-8671 (2003)
• [Publications] Fukuzumi, S. et al.: "Accelerating Effect of a Proton on the Reduction of CO_2 Dissolved in Water under Acidic Conditions. Isolation, Crystal Structure, and Reducing Ability of a Water-Soluble Ruthenium Hydride Complex"Journal of the American Chemical Society. 125・47. 14266-14267 (2003)
• [Publications] Fukuzumi, S. et al.: "Quaternary Self-Organization of Porphyrin and Fullerene Units by Clusterization with Gold Nanoparticles on SnO_2 Electrodes for Organic Solar Cells"Journal of the American Chemical Society. 125・49. 14962-14963 (2003)
• [Publications] Fukuzumi, S. et al.: "Effects of hydrogen bonding on metal ion-promoted intramolecular electron transfer and photoinduced electron transfer in a ferrocene-quinone dyad with a rigid amide spacer"Journal of the American Chemical Society. 125・4. 1007-1013 (2003)
• [Publications] Fukuzumi, S. et al.: "Mechanisms of Electron-Transfer Oxidation of NADH Analogues and Chemiluminescence. Detection of the Keto and Enol Radical Cations"Journal of the American Chemical Society. 125・16. 4808-4816 (2003)
• [Publications] Fukuzumi, S. et al.: "Mechanisms of Hydrogen-, Oxygen-, and Electron-Transfer Reactions of Cumylperoxyl Radical"Journal of the American Chemical Society. 125・30. 9074-9082 (2003)
• [Publications] Fukuzumi, S. et al.: "Metal-Centered Photoinduced Electron Transfer Reduction of a Gold(III) Porphyrin Cation Linked with a Zinc Porphyrin to Produce a Long-Lived Charge-Separated State in Nonpolar Solvents"Journal of the American Chemical Society. 125・49. 14984-14985 (2003)
• [Publications] Fukuzumi, S. et al.: "Isolation and Crystal Structure of a Water-Soluble Iridium Hydride : A Robust and Highly Active Catalyst for Acid-Catalyzed Transfer Hydrogenations of Carbonyl Compounds in Acidic Media"Journal of the American Chemical Society. 125・14. 4149-4154 (2003)
• [Publications] Fukuzumi, S. et al.: "Metal Ion-Promoted Intramolecular Electron Transfer in a Ferrocene-Naphthoquinone Linked Dyad. Continuous Change in Driving Force and Reorganization Energy with Metal Ion Concentration"Journal of the American Chemical Society. 125・23. 7014-7021 (2003)
• [Publications] Fukuzumi, S. et al.: "Excited-state deprotonation and H/D exchange of an iridium hydride complex"Angewandte Chemie, International Edition. 42・44. 5492-5495 (2003)
• [Publications] Fukuzumi, S. et al.: "A ruthenium pterin complex showing proton-coupled electron transfer : synthesis and characterization"Angewandte Chemie, International Edition. 42・40. 4951-4954 (2003)
• [Publications] Fukuzumi, S. et al.: "A Molecular Tetrad Allowing Efficient Energy Storage for 1.6 s at 163 K"Journal of Physical Chemistry A. 108・4. 541-548 (2004)
• [Publications] Fukuzumi, S. et al.: "Ultrafast Photodynamics of Exciplex Formation and Photoinduced Electron Transfer in Porphyrin-Fullerene Dyads Linked at Close Proximity"Journal of Physical Chemistry A. 107・42. 8834-8844 (2003)
• [Publications] Fukuzumi, S. et al.: "Formation of a Supramolecular Porphyrin-Spacer-Acceptor Ternary Complex and Intracomplex Electron Transfer"Journal of Physical Chemistry A. 107・3. 379-385 (2003)
• [Publications] Fukuzumi, S. et al.: "Strong Inhibition of Singlet Oxygen Sensitization in Pyridylferrocene-Fluorinated Zinc Porphyrin Supramolecular Complexes"Journal of Physical Chemistry A. 107・29. 5515-5522 (2003)
• [Publications] Fukuzumi, S. et al.: "Light Energy Conversion Using Mixed Molecular Nanoclusters. Porphyrin and C_<60> Cluster Films for Efficient Photocurrent Generation"Journal of Physical Chemistry B. 107・44. 12105-12112 (2003)
• [Publications] Fukuzumi, S. et al.: "Diels-Alder Reactions of Anthracenes with Dienophiles via Photo induced Electron Transfer"Journal of Physical Chemistry A. 107・28. 5412-5418 (2003)
• [Publications] Fukuzumi, S. et al.: "Driving Force Dependence of Photoinduced Electron Transfer Dynamics of Intercalated Molecules in DNA"Journal of Physical Chemistry B. 107・45. 12511-12518 (2003)
• [Publications] Fukuzumi, S. et al.: "Novel Photocatalytic Function of Porphyrin-Modified Gold Nanoclusters in Comparison with the Reference Porphyrin Compound"Journal of Physical Chemistry B. 107・43. 11979-11986 (2003)
• [Publications] Fukuzumi, S. et al.: "Oxygenation of a-Methylstyrene with Molecular Oxygen, Catalyzed by 10-Methylacridinium Ion via Photoinduced Electron Transfer"Journal of Physical Chemistry A. 107・22. 4339-4346 (2003)
• [Publications] Fukuzumi, S.: "Catalytic control of electron-transfer processes"Pure and Applied Chemistry. 75・5. 577-587 (2003)
• [Publications] Fukuzumi, S. et al.: "Seconds Lasting Charge-Separated State Generated in Ferrocene-meso, meso-Linked Porphyrin Trimer-FuHerene Pentad with a High Quantum Yield"Chemistry -A European Journal. (In press). (2004)
• [Publications] Fukuzumi, S. et al.: "Effects of metal ions on photoinduced electron transfer in zinc porphyrin-naphthalenediimide linked systems"Chemistry -A European Journal. 10・2. 474-483 (2004)
• [Publications] Fukuzumi, S. et al.: "Quantitative evaluation of d-p interaction in copper(I) complexes and control of copper(I)-dioxygen reactivity"Chemistry -A European Journal. 10・1. 237-246 (2004)
• [Publications] Fukuzumi, S. et al.: "Driving force dependence of intermolecular electron-transfer reactions of fullerenes"Chemistry -A European Journal. 9・7. 1585-1593 (2003)
• [Publications] Fukuzumi, S. et al.: "Reversed effects of DNA on hydride transfer and electron transfer reactions of acridinium and quinolinium ions"Chemical Communications. ・15. 1886-1887 (2003)
• [Publications] Fukuzumi, S. et al.: "Remarkable effects of counter ions on scandium ion-promoted electron ransfer treactions"Chemical Communications. ・9. 1070-1071 (2003)
• [Publications] Fukuzumi, S. et al.: "Enhancement of light harvesting and photocurrent generation by ITO electrodes modified with meso, meso-linked porphyrin oligomers"Nano Letters. 3・3. 409-412 (2003)
• [Publications] Fukuzumi, S. et al.: "Long-Lived Charge-Separated State Produced by Photoinduced Electron Transfer in a Zinc Imidazoporphyrin-C_<60> Dyad"Organic Letters. 5・15. 2719-2721 (2003)
• [Publications] Fukuzumi, S. et al.: "Structure and Photophysical Properties of Porphyrin-Modified Metal Nanoclusters with Different Chain Lengths"Langmuir. 20・1. 73-81 (2004)
• [Publications] Fukuzumi, S. et al.: "Substituent Effects on the Site of Electron Transfer during the First Reduction for Gold(III) Porphyrins"Inorganic.Chemistry. (In press). (2004)
• [Publications] Fukuzumi, S. et al.: "New perspective of electron transfer chemistry"Organic & Biomolecular Chemistry. 1・4. 609-620 (2003)
• [Publications] Fukuzumi, S. et al.: "Fast self-exchange electron transfer and delocalization of unpaired electron between zinc porphyrin radical cations and zinc porphyrins"Journal of Porphyrins and Phthalocyanines. 7・4&5. 328-336 (2003)
• [Publications] Fukuzumi, S. et al.: "A Planar Catechin Analogue as a Promising Antioxidant with Redused Prooxidant Activity"Chemical Research in Toxicology. 16・1. 81-86 (2003)
• [Publications] Fukuzumi, S. et al.: "πComplex Formation in Electron-Transfer Reactions of Porphyrins"Journal of Porphyrins and Phthalocyanines. (In press).
• [Publications] Fukuzumi, S. et al.: "Porphyrin and Fullerene-Based Molecular Photovoltaics"Advanced Functional Materials. (In press).
• [Publications] Fukuzumi, S. et al.: "Supramolecular Photovoltaic Cells of Porphyrin Dendrimers and Fullerene"Advanced Materials. (In press).
• [Publications] Fukuzumi, S. et al.: "Kinetic study of the electron-transfer oxidation of the phenolate anion of a vitamin E model by molecular oxygen generating superoxide anion in an aprotic medium"Organic & Biomolecular Chemistry. 1・22. 4085-4088 (2003)
• [Publications] Fukuzumi, S. et al.: "Nanostructured assembly of porphyrin clusters for light energy conversion"Journal of Materials Chemistry. 13・10. 2515-2520 (2003)
• [Publications] Fukuzumi, S. et al.: "Thermochromism of the disproportionation equilibrium of -dimer radical anion complexes bridged by scandium ions"Organic & Biomolecular Chemistry. 2・5. 642-644 (2004)
• [Publications] Fukuzumi, S. et al.: "A Planar Catechin Analogue Having a More Negative Oxidation Potential than (+)- Catechin as an Electron Transfer Antioxidant against a Peroxyl Radical"Chemical Research in Toxicology. 17・1. 26-31 (2004)
• [Publications] Fukuzumi, S. et al.: "Layer-by-layer assembly of porphyrin-fullerene dyads"Journal of Porphyrins and Phthalocyanines. 7・4&5. 357-364 (2003)
• [Publications] Fukuzumi, S. et al.: "Molecular Engineering of Myoglobin : Influence of Residue 68 on the Rate and the Enantioselectivity of Oxidation Reactions Catalyzed by H64D/V68X Myoglobin"Biochemistry. 42・34. 10174-10181 (2003)
• [Publications] Fukuzumi, S. et al.: "Fluorinated photosensitizers : synthesis, photophysical, electrochemical, intracellular localization, in vitro photosensitizing efficacy and determination of tumor-untake by 19F in vivo NMR spectroscopy"Tetrahedron. 59・50. 10059-10073 (2003)
• [Publications] Fukuzumi, S. et al.: "Synthesis and Structural, Electrochemical, and Optical Properties of Ru(II) Complexes with Azobis(2,2'-bipyridine)s"Inorganic Chemistry. 42・9. 3057-3066 (2003)
• [Publications] Fukuzumi, S. et al.: "Quantitative Evaluation of Lewis Acidity of Metal Ions with Different Ligands and Counterions in Relation to the Promoting Effects of Lewis Acids on Electron Transfer Reduction of Oxygen"Journal of Organic Chemistry. 68・12. 4720-4726 (2003)
• [Publications] Fukuzumi, S. et al.: "Efficient radical scavenging ability of artepillin C, a major component of Brazilian propolis, and the mechanism"Organic & Biomolecular Chemistry. 1・9. 1452-1454 (2003)
• [Publications] Fukuzumi, S. et al.: "Kinetic study of the electron-transfer oxidation of the phenolate anion of a vitamin E model by molecular oxygen generating superoxide anion in an aprotic medium"Organic & Biomolecular Chemistry. 1・22. 4085-4088 (2003)
• [Publications] Fukuzumi, S. et al.: "C_<70> vs. C_<60> in zinc porphyrin-fullerene dyads : Prolonged charge separation and ultrafast energy transfer from the second excited singlet state of porphyrin,"Photochemical & Photobiological Sciences. 2・3. 251-258 (2003)
• [Publications] Fukuzumi, S. et al.: "Metal and size effects on structures and photophysical properties of porphyrin-modified metal nanoclusters"Journal of Materials Chemistry. 13・12. 2890-2898 (2003)
• [Publications] Fukuzumi, S. et al.: "Structure and photoelectrochemical properties of ITO electrodes modified with self-assembled monolayers of meso, meso-linked porphyrin oligomers"Journal of Porphyrins and Phthalocyanines. 7・4&5. 296-312 (2003)
• [Publications] Fukuzumi, S. et al.: "Fullerenes--Volume 13 : Fullerenes and Nanotubes"Electrochemical Society. 27 (2003)
• [Publications] Fukuzumi, S.: "Sentan Kagaku Shirizu"丸善(株). 10 (2003)
• [Publications] Fukuzumi, S.: "Molecular and Supramolecular Photochemistry"Marcel dekker Inc.. 47 (2003)
• [Publications] Fukuzumi, S.: "Tanpakushitsu Kakusan Koso 48 (11,Zokango)"共立出版(株). 7 (2003)
• [Publications] Fukuzumi, S.: "Gendai Kagaku 393"(株)東京化学同人. 6 (2003)