2000 年度実績報告書

フラーレンの電子移動化学と応用

研究課題

研究課題/領域番号	11694079
研究機関	大阪大学
研究代表者	福住俊一大阪大学, 大学院・工学研究科, 教授 (40144430)
研究分担者	伊東忍大阪市立大学, 大学院・理学研究科, 教授 (30184659) 末延知義大阪大学, 大学院・工学研究科, 助手 (90271030) 今堀博大阪大学, 大学院・工学研究科, 助教授 (90243261)
キーワード	フラーレン / 電子移動 / ラジカルアニオン / 電子スピン共鳴 / 対称性 / X線結晶構造解析 / フラーレン付加体 / 縮重
研究概要	フラーレンC_<60>は、その発見当初から高い対称性を有する特異な構造が注目され、これまでの数多くのC_<60>誘導体化法の開発によって、C_<60>骨格の対称性を様々に変化させることも可能となってきた。有機ラジカルの構造とその電子状態についての関係を知る目的にはESRが最も有力な実験的手法となるが、フラーレン誘導体のラジカルアニオン種の構造と電子状態の関係についての系統的実験研究は、これまでなされていなかった。そこで、本研究では、様々なフラーレン誘導体を化学的、または電気化学的に還元してラジカルアニオンとし、その分光特性について検討した。脱酸素ベンゾニトリル中、C_<60>(I_h対称)をテトラメチルセミキノンラジカルアニオンにより還元して得られるC_<60>^-のESRは298Kにおいてg=1.9984に幅広いシグナルを示す。C_<60>ジベンジル付加体ラジカルアニオンのESRでは、C_<60>^-よりもg値は大きくなり、線幅(ΔH_<msl>)は減少した。同じC_<60>ジベンジル付加体でも、1,2-付加体(C_<2V>対称)よりも対称性の低い1,4-付加体(C_s対称)の方がΔH_<mst>が小さいことが分かった。C_<60>テトラベンジル付加体(C_1対称)は、C_<60>ジベンジル付加体よりもさらに対称性が低下し、g値は2.0010と最も大きくなり、ΔH_<msl>は最も小さくなった(0.17G)。この場合、2つの非等価なプロトンに由来する超微細構造が観測された。C_<60>は対称性が高くLOMO軌道が3重縮重しているが、官能基の付加による対称性の低下に伴い、縮重が解け、LUMOとLUMO+1間のエネルギーギャップ(δ)が大きくなることがわかった。

研究成果

(32件)

すべてその他

すべて文献書誌 (32件)

[文献書誌] Shunichi Fukuzumi et al.: "Light-Harvesting and Photocurrent Generation by Gold Electrodes Modified with Mixed Self-Assembled Monolayers of Boron-Dipyrrin and Ferrocene-Porphyrin-Fullerene Triad"J.Am.Chem.Soc.. 123・1. 100-110 (2001)
[文献書誌] Shunichi Fukuzumi et al.: "Photoactive Three-Dimensional Monolayers : Porphyrin-Alkanethiolate-Stabilized Gold Clusters"J.Am.Chem.Soc.. 123・2. 335-336 (2001)
[文献書誌] Shunichi Fukuzumi et al.: "Catalytic Effects of Dioxygen on Intramolecular Electron Transfer in Radical Ion Pairs of Zinc Porphyrin-Linked Fullerenes"J.Am.Chem.Soc.. 123・(in press). (2001)
[文献書誌] Shunichi Fukuzumi et al.: "Effects of Metal Ions on Physicochemical Properties and Redox Reactivity of Phenolates and Phenoxyl Radicals : Mechanistic Insight into Hydrogen Atom Abstraction by Phenoxyl Radical-Metal Complexes"J.Am.Chem.Soc.. 123・(in press). (2001)
[文献書誌] Shunichi Fukuzumi et al.: "Modulating Charge Separation and Charge Recombination Dynamics in Porphyrin-Fullerene Linked Dyads and Triads : Marcus-Normal versus Inverted Region,"J.Am.Chem.Soc.. 123・(in press). (2001)
[文献書誌] Shunichi Fukuzumi et al.: "Effects of Metal Ions on the Electronic, Redox, and Catalytic Properties of Cofactor TTQ of Quinoprotein Amine Dehydrogenases"J.Am.Chem.Soc.. 122・49. 12087-12097 (2000)
[文献書誌] Shunichi Fukuzumi et al.: "Photochemical Reactions of Coenzyme PQQ (Pyrroloquinolinequinone) and Analogues with Benzyl Alcohol Derivatives via Photoinduced Electron Transfer"J.Am.Chem.Soc.. 122・35. 8435-8443 (2000)
[文献書誌] Shunichi Fukuzumi et al.: "Hydride Transfer from 9-Substituted 10-Methyl-9,10-dihydroacridines to Hydride Acceptors via Charge-Transfer Complexes and Sequential Electron-Proton-Electron Transfer.A Negative Temperature Dependence of the Rates"J.Am.Chem.Soc.. 122・18. 4286-4294 (2000)
[文献書誌] Shunichi Fukuzumi et al.: "Stepwise Bond Formation in Photochemical and Thermal Diels-Alder Reactions of C_<60> with Danishefsky's Dienes"J.Am.Chem.Soc.. 122・10. 2236-2243 (2000)
[文献書誌] Shunichi Fukuzumi et al.: "Resonance Raman Spectroscopy as a Probe of the Bis (μ-oxo) dicopper Core"J.Am.Chem.Soc.. 122・5. 792-802 (2000)
[文献書誌] Shunichi Fukuzumi et al.: "Synthesis and Characterization of Imidazolate-Bridged Dinuclear Complexes as Active Site Models of Cu,Zn-SOD"J.Am.Chem.Soc.. 122・24. 5733-5741 (2000)
[文献書誌] Shunichi Fukuzumi et al.: "Electrosynthesis and Structural Characterization of Two (C_6H_5CH_2)_4C_<60> Isomers"J.Am.Chem.Soc.. 122・4. 563-570 (2000)
[文献書誌] Shunichi Fukuzumi et al.: "Photoinduced energy transfer in mixed self-assembled monolayers of pyrene and porphyrin"Chem.Commun.. ・8. 661-662 (2000)
[文献書誌] Shunichi Fukuzumi et al.: "Catalytic effect of monovalent cations on the amine oxidation by cofactor TTQ of quinoprotein amine dehydrogenases"Chem.Commun.. ・5. 329-330 (2000)
[文献書誌] Shunichi Fukuzumi et al.: "Regioreversed Thermal and Photochemical Reduction of 10-Methylacridinium and 1-Methylquinolinium Ions by Organosilanes and Oraganostannanes"J.Phys.Chem.A. 105・(in press). (2001)
[文献書誌] Shunichi Fukuzumi et al.: "An Extremely Small Reorganization Energy of Electron Transfer in Porphyrin-Fullerene Dyad"J.Phys.Chem.A. 105・(in press). (2001)
[文献書誌] Shunichi Fukuzumi et al.: "Solvent Dependence of Charge Separation and Charge Recombination Rates in Porphyrin-Fullerene Dyad"J.Phys.Chem.A. 105・2. 325-332 (2001)
[文献書誌] Shunichi Fukuzumi et al.: "Effects of Lowering Symmetry on the ESR Spectra of Radical Anions of Fullerene Derivatives and the Reduction Potentials"J.Phys.Chem.A. 104・46. 10688-10694 (2000)
[文献書誌] Shunichi Fukuzumi et al.: "Effect of Addition Pattern on the Electrochemical and Spectroscopic Properties of Neutral and Reduced 1,2-and1,4-(C_6H_5CH_2)_2C_<60> Isomers"J.Phys.Chem.A. 104・17. 3878-3883 (2000)
[文献書誌] Shunichi Fukuzumi et al.: "Splitting of Degenerate Orbitals of Dibenzyl and Tetrabenzyl Adducts of C_<60> : ESR of the Radical Anions and the Rotation Barriers of Benzyl Groups"J.Phys.Chem.A. 104・13. 2908-2913 (2000)
[文献書誌] Shunichi Fukuzumi et al.: "Electrogeneration and Characterization of(C_6H_5CH_2)_2C_<70>"J.Phys.Chem.A. 104・13. 2902-2907 (2000)
[文献書誌] Shunichi Fukuzumi et al.: "Comparison between Electron Transfer and Nucleophilic Reactivities of Ketene Silyl Acetals with Cationic Electrophiles"J.Org.Chem.. 66・4. 1450-1454 (2001)
[文献書誌] Shunichi Fukuzumi et al.: "Photochemical Generation of Cyclopentadienyliron Dicarbonyl Anion by a Nicotinamide Adenine Dinucleotide Dimer Analogue"Inorg.Chem.. 40・(in press). (2001)
[文献書誌] Shunichi Fukuzumi et al.: "Model Complexes for the Active Form of Galactose Oxidase.Physicochemical Properties of Cu (II)-and Zn(II)-Phenoxyl Radical Complexes"Inorg.Chem.. 39・16. 3708-3711 (2000)
[文献書誌] Shunichi Fukuzumi et al.: "100% Selective Oxygenation of p-Xylene to p-Tolualdehyde via Photoinduced Electron Transfer"Org.Lett.. 2・23. 3647-3650 (2000)
[文献書誌] Shunichi Fukuzumi et al.: "Aliphatic Hydroxylation by a Bis(μ-oxo)dicopper (III) Complex"Angew.Chem.Int.Ed.. 39・2. 398-400 (2000)
[文献書誌] Shunichi Fukuzumi et al.: "Quantitative Evaluation of Lewis Acidity of Metal Ions Derived from the g Values of ESR Spectra of Superoxide : Metal Ion Complexes in Relation to the Promoting Effects in Electron Transfer Reactions"Chem.Eur.J. 6・24. 4532-4535 (2000)
[文献書誌] Shunichi Fukuzumi et al.: "The Essential Role of a Zn^<II> Ion in the Disproportionation of Semiquinone Radical Anion by an Imidazolate-Bridged Cu^<II>-Zn^<II> Model of Superoxide Dismutase"Angew.Chem.Int.Ed.. 39・24. 4537-4539 (2000)
[文献書誌] Shunichi Fukuzumi et al.: "Characterization of Imidazolate-bridged Cu (II) -Zn (II) Heterodinuclear and Cu (II) -Cu (II) Homodinuclear Hydroperoxo Complexes as Reaction Intermediate Models of Cu, Zn-SOD"Chem.Commun.. ・12. 1051-1052 (2000)
[文献書誌] Shunichi Fukuzumi et al.: "Remarkable enhancement of photocurrent generation by ITO electrodes modified with a self-assembled monolayer of porphyrin"Chem.Commun.. ・19. 1921-1922 (2000)
[文献書誌] Shunichi Fukuzumi et al.: "Electron Transfer in Chemistry,Vol.2"Wiley-VCH(in press). (2001)
[文献書誌] Shunichi Fukuzumi et al.: "Electron Transfer in Chemistry,Vol.4"Wiley-VCH(in press). (2001)

2000 年度 実績報告書

フラーレンの電子移動化学と応用

研究代表者

福住 俊一 大阪大学, 大学院・工学研究科, 教授 (40144430)

研究成果

[文献書誌] Shunichi Fukuzumi et al.: "Light-Harvesting and Photocurrent Generation by Gold Electrodes Modified with Mixed Self-Assembled Monolayers of Boron-Dipyrrin and Ferrocene-Porphyrin-Fullerene Triad"J.Am.Chem.Soc.. 123・1. 100-110 (2001)

[文献書誌] Shunichi Fukuzumi et al.: "Photoactive Three-Dimensional Monolayers : Porphyrin-Alkanethiolate-Stabilized Gold Clusters"J.Am.Chem.Soc.. 123・2. 335-336 (2001)

[文献書誌] Shunichi Fukuzumi et al.: "Catalytic Effects of Dioxygen on Intramolecular Electron Transfer in Radical Ion Pairs of Zinc Porphyrin-Linked Fullerenes"J.Am.Chem.Soc.. 123・(in press). (2001)

[文献書誌] Shunichi Fukuzumi et al.: "Effects of Metal Ions on Physicochemical Properties and Redox Reactivity of Phenolates and Phenoxyl Radicals : Mechanistic Insight into Hydrogen Atom Abstraction by Phenoxyl Radical-Metal Complexes"J.Am.Chem.Soc.. 123・(in press). (2001)

[文献書誌] Shunichi Fukuzumi et al.: "Modulating Charge Separation and Charge Recombination Dynamics in Porphyrin-Fullerene Linked Dyads and Triads : Marcus-Normal versus Inverted Region,"J.Am.Chem.Soc.. 123・(in press). (2001)

[文献書誌] Shunichi Fukuzumi et al.: "Effects of Metal Ions on the Electronic, Redox, and Catalytic Properties of Cofactor TTQ of Quinoprotein Amine Dehydrogenases"J.Am.Chem.Soc.. 122・49. 12087-12097 (2000)

[文献書誌] Shunichi Fukuzumi et al.: "Photochemical Reactions of Coenzyme PQQ (Pyrroloquinolinequinone) and Analogues with Benzyl Alcohol Derivatives via Photoinduced Electron Transfer"J.Am.Chem.Soc.. 122・35. 8435-8443 (2000)

[文献書誌] Shunichi Fukuzumi et al.: "Hydride Transfer from 9-Substituted 10-Methyl-9,10-dihydroacridines to Hydride Acceptors via Charge-Transfer Complexes and Sequential Electron-Proton-Electron Transfer.A Negative Temperature Dependence of the Rates"J.Am.Chem.Soc.. 122・18. 4286-4294 (2000)

[文献書誌] Shunichi Fukuzumi et al.: "Stepwise Bond Formation in Photochemical and Thermal Diels-Alder Reactions of C_<60> with Danishefsky's Dienes"J.Am.Chem.Soc.. 122・10. 2236-2243 (2000)

[文献書誌] Shunichi Fukuzumi et al.: "Resonance Raman Spectroscopy as a Probe of the Bis (μ-oxo) dicopper Core"J.Am.Chem.Soc.. 122・5. 792-802 (2000)

[文献書誌] Shunichi Fukuzumi et al.: "Synthesis and Characterization of Imidazolate-Bridged Dinuclear Complexes as Active Site Models of Cu,Zn-SOD"J.Am.Chem.Soc.. 122・24. 5733-5741 (2000)

[文献書誌] Shunichi Fukuzumi et al.: "Electrosynthesis and Structural Characterization of Two (C_6H_5CH_2)_4C_<60> Isomers"J.Am.Chem.Soc.. 122・4. 563-570 (2000)

[文献書誌] Shunichi Fukuzumi et al.: "Photoinduced energy transfer in mixed self-assembled monolayers of pyrene and porphyrin"Chem.Commun.. ・8. 661-662 (2000)

[文献書誌] Shunichi Fukuzumi et al.: "Catalytic effect of monovalent cations on the amine oxidation by cofactor TTQ of quinoprotein amine dehydrogenases"Chem.Commun.. ・5. 329-330 (2000)

[文献書誌] Shunichi Fukuzumi et al.: "Regioreversed Thermal and Photochemical Reduction of 10-Methylacridinium and 1-Methylquinolinium Ions by Organosilanes and Oraganostannanes"J.Phys.Chem.A. 105・(in press). (2001)

[文献書誌] Shunichi Fukuzumi et al.: "An Extremely Small Reorganization Energy of Electron Transfer in Porphyrin-Fullerene Dyad"J.Phys.Chem.A. 105・(in press). (2001)

[文献書誌] Shunichi Fukuzumi et al.: "Solvent Dependence of Charge Separation and Charge Recombination Rates in Porphyrin-Fullerene Dyad"J.Phys.Chem.A. 105・2. 325-332 (2001)

[文献書誌] Shunichi Fukuzumi et al.: "Effects of Lowering Symmetry on the ESR Spectra of Radical Anions of Fullerene Derivatives and the Reduction Potentials"J.Phys.Chem.A. 104・46. 10688-10694 (2000)

[文献書誌] Shunichi Fukuzumi et al.: "Effect of Addition Pattern on the Electrochemical and Spectroscopic Properties of Neutral and Reduced 1,2-and1,4-(C_6H_5CH_2)_2C_<60> Isomers"J.Phys.Chem.A. 104・17. 3878-3883 (2000)

[文献書誌] Shunichi Fukuzumi et al.: "Splitting of Degenerate Orbitals of Dibenzyl and Tetrabenzyl Adducts of C_<60> : ESR of the Radical Anions and the Rotation Barriers of Benzyl Groups"J.Phys.Chem.A. 104・13. 2908-2913 (2000)

[文献書誌] Shunichi Fukuzumi et al.: "Electrogeneration and Characterization of(C_6H_5CH_2)_2C_<70>"J.Phys.Chem.A. 104・13. 2902-2907 (2000)

[文献書誌] Shunichi Fukuzumi et al.: "Comparison between Electron Transfer and Nucleophilic Reactivities of Ketene Silyl Acetals with Cationic Electrophiles"J.Org.Chem.. 66・4. 1450-1454 (2001)

[文献書誌] Shunichi Fukuzumi et al.: "Photochemical Generation of Cyclopentadienyliron Dicarbonyl Anion by a Nicotinamide Adenine Dinucleotide Dimer Analogue"Inorg.Chem.. 40・(in press). (2001)

[文献書誌] Shunichi Fukuzumi et al.: "Model Complexes for the Active Form of Galactose Oxidase.Physicochemical Properties of Cu (II)-and Zn(II)-Phenoxyl Radical Complexes"Inorg.Chem.. 39・16. 3708-3711 (2000)

[文献書誌] Shunichi Fukuzumi et al.: "100% Selective Oxygenation of p-Xylene to p-Tolualdehyde via Photoinduced Electron Transfer"Org.Lett.. 2・23. 3647-3650 (2000)

[文献書誌] Shunichi Fukuzumi et al.: "Aliphatic Hydroxylation by a Bis(μ-oxo)dicopper (III) Complex"Angew.Chem.Int.Ed.. 39・2. 398-400 (2000)

[文献書誌] Shunichi Fukuzumi et al.: "Quantitative Evaluation of Lewis Acidity of Metal Ions Derived from the g Values of ESR Spectra of Superoxide : Metal Ion Complexes in Relation to the Promoting Effects in Electron Transfer Reactions"Chem.Eur.J. 6・24. 4532-4535 (2000)

[文献書誌] Shunichi Fukuzumi et al.: "The Essential Role of a Zn^<II> Ion in the Disproportionation of Semiquinone Radical Anion by an Imidazolate-Bridged Cu^<II>-Zn^<II> Model of Superoxide Dismutase"Angew.Chem.Int.Ed.. 39・24. 4537-4539 (2000)

[文献書誌] Shunichi Fukuzumi et al.: "Characterization of Imidazolate-bridged Cu (II) -Zn (II) Heterodinuclear and Cu (II) -Cu (II) Homodinuclear Hydroperoxo Complexes as Reaction Intermediate Models of Cu, Zn-SOD"Chem.Commun.. ・12. 1051-1052 (2000)

[文献書誌] Shunichi Fukuzumi et al.: "Remarkable enhancement of photocurrent generation by ITO electrodes modified with a self-assembled monolayer of porphyrin"Chem.Commun.. ・19. 1921-1922 (2000)

[文献書誌] Shunichi Fukuzumi et al.: "Electron Transfer in Chemistry,Vol.2"Wiley-VCH(in press). (2001)

[文献書誌] Shunichi Fukuzumi et al.: "Electron Transfer in Chemistry,Vol.4"Wiley-VCH(in press). (2001)

2000 年度実績報告書

福住俊一大阪大学, 大学院・工学研究科, 教授 (40144430)