1989 年度実績報告書

光誘起電子移動及び関連現象のダイナミックスとメカニズム

研究課題

研究課題/領域番号	62065006
研究機関	大阪大学
研究代表者	又賀昇大阪大学, 基礎工学部, 教授 (30029368)
研究分担者	宮坂博大阪大学, 基礎工学部, 助手 (40182000) 平田善則大阪大学, 基礎工学部, 助手 (90135674) 岡田正大阪大学, 基礎工学部, 助教授 (40029442)
キーワード	エネルギーギャップ則 / 光誘起CSとCR / 光合成反応中心 / 水素引抜き / ピコ秒多光子イオン化
研究概要	(1)電子移動のエネルギーギャップ則につき以前に提出した新しい理論をより厳密な反応座標に基いて定式化した。この場合にも光誘起電荷分離のエネルギーギャップ依存性を説明するためには、誘電飽和を考慮することが必要であることを示した。(2)同一クロモフォア間での光誘起電荷分離(CS)に関し、9、9'ービアントリル(BA)の他に、1、2ージアントリルエタンでも起ることをピコ秒分光によるイオン対状態の直接測定で示し、この場合にはアントラセン間相互作用がBAの場合より弱いため、より完全なCS状態が観測されることを示した。またこの系は光合成反応中心のクロロフィルダイマーでの光CSのモデルとしても興味深い。(3)光合成反応中心における光CSのモデルとして、ポルフィリンに4このビオローゲン基をメソ位に結合した系のピコ・ナノ秒レーザー分光による研究を行い、S_1状態からの速いCSによって生成した分子内ラジカルイオン対状態の再結合(CR)には6.4μsかかることを見出した。(4)ピレンやアントラセンとN、Nージメチルアニリンをメチレン鎖であるいは直接一重結合でつないだ系(Pn、An)の光CSとCRをフェムト秒、ピコ秒分光で調べ、大部分は通常の弱い相互作用による電子移動理論で説明できるが、A_0はA_1よりCSがおそく、通常の理論で説明できないことを示した。またこれと類似のことはTCNBと芳香族炭化水素のCT錯体の励起FC状態からのイオン対状態生成でもみられ、相互作用がある程度以上強くなると構造変化が必要なためCSがおそくなることを示した。(5)無極性溶媒中における芳香族ジアミンのピコ秒多光子イオン化によるカチオンー電子対のCR過程を直接観測してthermalization lengthを求めた。(6)三重項ベンゾフェノンーアミン水素引抜きの機構をフェムト秒、ピコ秒分光で調べ、アミンの性質に依存して、比較的長寿命のイオン対における陽子移動や直接水素移動等種々の場合があることを明らかにした。

研究成果

(35件)

すべてその他

すべて文献書誌 (35件)

[文献書誌] N.Mataga: "Picosecond Dynamics of Intramolecular Electron and Energy Transfer in Porphyrin Dimer Model Compounds" Chem.Phys.131. 473-480 (1989)
[文献書誌] H.Miyasaka: "Femtosecond-Picosecond Laser Photolysis Studies of Ion Pair Formation Process in the Excited State of Charge Transfer Complex in Solution" J.Phys.Chem.93. 3380-3382 (1989)
[文献書誌] N.Mataga: "Charge Transfer Rates in Symmetric and Symmetry-Disturbed Derivatives of 9,9'-Bianthryl" J.Phys.Chem.93. 3383-3386 (1989)
[文献書誌] T.Ohno: "Backward Electron Transfers within Geminate Radical Pairs Formed by Electron-Transfer Quenching of Phosphorescent States of Tris(2,2'-bipyrazine)ruthenium(II)and Tris(4-methyl-2-(2'-pyridyl)pyrimidine)ruthenium(II)" J.Phys.Chem.93. 3546-3551 (1989)
[文献書誌] A.Yoshimori: "Transfer Coefficient in Electrochemical Reactions" J.Phys.Chem.93. 3694-3702 (1989)
[文献書誌] Y.Hirata: "Dynamic Behavior of Solvated Electron Produced by Photoionization of Indole and Tryptophane in Several Polar Solvents" J.Phys.Chem.93. 4527-4530 (1989)
[文献書誌] N.Mataga: "Picosecond Laser Photolysis Studies on Dimer Model Systems in Relation to Photosynthetic Charge Separation Processes" Tetrahedron. 45. 4683-4692 (1989)
[文献書誌] T.Asahi: "Charge Recombination Process of Ion Pair State Produced by Excitation of Charge-Transfer Complex in Acetonitrile Solution.Essentially Different Character of Its Energy Gap Dependence from That of Geminate Ion Pair Formed by Encounter between Fluorescer and Quencher" J.Phys.Chem.93. 6575-6578 (1989)
[文献書誌] H.Yao: "Solvation Induced Charge Separation in the Excited State of Composite Systems with Identical Halves and Intramolecular Excimer Formation by Recombination-Picosecond Laser Photolysis Studies on 1,2-Dianthrylethanes" J.Phys.Chem.93. 7388-7394 (1989)
[文献書誌] Y.Sakata: "Synthesis of Completely Fixed Porphyrin-Quinone Compounds and the Mutual Orientation Effect on Electron Transfer" J.Am.Chem.Soc.111. 8979-8981 (1989)
[文献書誌] Y.Hirata: "Direct Observation of Electron-Cation Geminate Pair Produced By Picosecond Laser Pulse Excitation in Several Nonpolar Solvents" J.Phys.Chem.93. 7539-7542 (1989)
[文献書誌] A.Yoshimori: "Shapes of the Electron-Transfer Rate vs Energy Gap Relations in Polar Solutions" J.Phys.Chem.93. 8316-8323 (1989)
[文献書誌] N.Ikeda: "Intramolecular Excimer Formation of the Diastereoisomers of Bis[1-(2-Pyrenyl)Ethyl]Ether as Revealed by Picosecond Time-Resolved Absorption Spectroscopy" Chem.Phys.Lett.154. 207-211 (1989)
[文献書誌] H.Kobashi: "Ion-Pair Formation Competing with Internal Conversion from the Second Excited State in the Chloranil-Diphenyl-amine Complex" Chem.Phys.Lett.160. 261-266 (1989)
[文献書誌] T.Kakitani: "Role of Protein Media in the Electron Transfer Reaction" Photosynthetic Research. 22. 187-193 (1989)
[文献書誌] J.D.Batteas: "Photoinduced Charge Separation in a Porphyrin-Tetra-viologen Supramolecular Array" J.Am.Chem.Soc.112. 126-133 (1990)
[文献書誌] H.Miyasaka: "Picosecond Laser Photolysis Studies on the Photoreduction of Excited Benzophenone by Diphenylamine in Solutions" Bull.Chem.Soc.Jpn.63. 131-137 (1990)
[文献書誌] N.Mataga: "Femtosecond-Picosecond Laser Photolysis Studies on the Photoinduced Charge Separation and Charge Recombination of Produced Ion Pair State of Some Typical Intramolecular Exciplex Compounds in Alkanenitrile Solvents" J.Phys.Chem.94. (1990)
[文献書誌] H.Miyasaka: "Picosecond 266 nm Multiphoton Laser Photolysis Studies on Liquid Alkane Solution of Aromatic Hydrocarbons:Ultre-fast Solute Triplet Formation" J.Phys.Chem.64. (1990)
[文献書誌] S.Ojima: "Femtosecon-Picosecond Laser Photolysis Studies on the Dynamics of Excited Charge Transfer Complexes in Solution.I.Charge Separation Processes in the Course of the Relaxation from the Excited Franck-Condon State of 1,2,4,5-Tetracyanobenzene in Benzene and Methyl-substituted Benzene Solutions" J.Phys.Chem.94. (1990)
[文献書誌] S.Kinoshita: "Solvent Relaxation Effect on Transient Hole-Burning Spectra of Organic Dyes" Chem.Phys.Lett.(1990)
[文献書誌] A.Harriman: "Photoinduced Intramolecular Electron Transfer in Isomeric Porphyrin-Monoviologen Complexes" J.Phys.Chem.(1990)
[文献書誌] A.Osuka: "Geometry Dependence of Intramolecular Photoinduced Electron Transfer in Synthetic Zinc-Ferric Hybrid Diporphyrins" J.Am.Chem.Soc.
[文献書誌] S.Ojima: "Femtosecond-Picosecond Laser Photolysis Studies on the Dynamics of Excited Charge Transfer Complexes in Solution.II.Ion Pair Formation Processes in the Excited State of 1,2,4,5-Tetracyanobenzene-Aromatic Hydrocarbon Complexes in Polar Solvents" J.Phys.Chem.
[文献書誌] Y.Hirata: "Monophotonic Ionization from the Vibrationally Unrelaxed Excited Singlet State of N,N,N',N'-Tetramethyl-p-pheny-lenediamine in Acetonitrile Solution" J.Phys.Chem.
[文献書誌] Y.Hirata: "Monophotonic Ionization of Benzidine Derivatives in Polar Solvents Studied by Picosecond Transient Absorption Measurements" Chem.Phys.Lett.
[文献書誌] N.Mataga: "Dynamics and Mechanisms of Photoinduced Charge Separation and Charge Recombination of Transient Ion Pair States-Femtosecond〜Picosecond Laser Photolysis Studies" Advances in Chemistry Series,Am.Chem.Soc.“Electron Transfer in Inorganic,Organic and Biological Systems".
[文献書誌] T.Kakitani: "Theoretical Analysis of Energy Gap Laws of Electron Trnasfer Reactions by Considering the Distribution of the Donor and Acceptor Distance" Advances in Chemistry Series,Am.Chem.Soc.“Electron Transfer in Inorganic,Organic and Biological Systems".
[文献書誌] N.Mataga: "Dynamics and Energy Gap Dependences of Photoinduced Charge Separation and Recombination of the Produced Ion Pair State" Photochemical Energy Conversion,Eds.J.R.Norris & D.Meisel,Elsevier. 32-46 (1989)
[文献書誌] N.Mataga: "Excitation Energy Transfer and Photoinduced Electron Transfer Phenomena in Some Confined Systems" Molecular Dynamics in Restricted Geometries,Eds.J.Klafter & J.Drake,John-Wiley. 23-37 (1989)
[文献書誌] F.Tanaka: "Dynamics of Excited State Relaxations in Some Proteins" Photochemistry on Solid Surface,Eds.M.Anpo & T.Matsuura,Elsevier. 551-565 (1989)
[文献書誌] N.Mataga: "Photoinduced Electron Transfer,Electron Photoejection and Related Phenomena in Solutions-Femtosecond〜Nanosecond Laser Photolysis Studies" Advances in Multi-Photon Processes and Spectroscopy,Vol.5,Ed.S.H.Lin,World Scientific. 175-276 (1989)
[文献書誌] 又賀昇: "光電子移動及び関連現象のダイナミックスとメカニズムーフェムト秒、ピコ秒分光による研究" 電気化学および工業物理化学. 57. 1025-1030 (1989)
[文献書誌] N.Mataga: "Femtosecond-Picosecond Laser Photolysis Studies on Electron Transfer Dynamics and Mechanisms in Some Model Systems" Proc.Jerusalem Symposium on Quantum Chemistry and Biochemistry Vol.22:Perspectives in Photosynthesis,Eds.J.Jortner & B.Pullman,Kluwer Academic. 227-240 (1990)
[文献書誌] H.Miyasaka: "Picosecond Ultraviolet Multiphoton Laser Photolysis Related to Radiolysis" Pulse Radiolysis of Irradiated Systems,Ed.Y.Tabata,CRC.

1989 年度 実績報告書

光誘起電子移動及び関連現象のダイナミックスとメカニズム

研究代表者

又賀 昇 大阪大学, 基礎工学部, 教授 (30029368)

研究成果

[文献書誌] N.Mataga: "Picosecond Dynamics of Intramolecular Electron and Energy Transfer in Porphyrin Dimer Model Compounds" Chem.Phys.131. 473-480 (1989)

[文献書誌] H.Miyasaka: "Femtosecond-Picosecond Laser Photolysis Studies of Ion Pair Formation Process in the Excited State of Charge Transfer Complex in Solution" J.Phys.Chem.93. 3380-3382 (1989)

[文献書誌] N.Mataga: "Charge Transfer Rates in Symmetric and Symmetry-Disturbed Derivatives of 9,9'-Bianthryl" J.Phys.Chem.93. 3383-3386 (1989)

[文献書誌] T.Ohno: "Backward Electron Transfers within Geminate Radical Pairs Formed by Electron-Transfer Quenching of Phosphorescent States of Tris(2,2'-bipyrazine)ruthenium(II)and Tris(4-methyl-2-(2'-pyridyl)pyrimidine)ruthenium(II)" J.Phys.Chem.93. 3546-3551 (1989)

[文献書誌] A.Yoshimori: "Transfer Coefficient in Electrochemical Reactions" J.Phys.Chem.93. 3694-3702 (1989)

[文献書誌] Y.Hirata: "Dynamic Behavior of Solvated Electron Produced by Photoionization of Indole and Tryptophane in Several Polar Solvents" J.Phys.Chem.93. 4527-4530 (1989)

[文献書誌] N.Mataga: "Picosecond Laser Photolysis Studies on Dimer Model Systems in Relation to Photosynthetic Charge Separation Processes" Tetrahedron. 45. 4683-4692 (1989)

[文献書誌] H.Yao: "Solvation Induced Charge Separation in the Excited State of Composite Systems with Identical Halves and Intramolecular Excimer Formation by Recombination-Picosecond Laser Photolysis Studies on 1,2-Dianthrylethanes" J.Phys.Chem.93. 7388-7394 (1989)

[文献書誌] Y.Sakata: "Synthesis of Completely Fixed Porphyrin-Quinone Compounds and the Mutual Orientation Effect on Electron Transfer" J.Am.Chem.Soc.111. 8979-8981 (1989)

[文献書誌] Y.Hirata: "Direct Observation of Electron-Cation Geminate Pair Produced By Picosecond Laser Pulse Excitation in Several Nonpolar Solvents" J.Phys.Chem.93. 7539-7542 (1989)

[文献書誌] A.Yoshimori: "Shapes of the Electron-Transfer Rate vs Energy Gap Relations in Polar Solutions" J.Phys.Chem.93. 8316-8323 (1989)

[文献書誌] N.Ikeda: "Intramolecular Excimer Formation of the Diastereoisomers of Bis[1-(2-Pyrenyl)Ethyl]Ether as Revealed by Picosecond Time-Resolved Absorption Spectroscopy" Chem.Phys.Lett.154. 207-211 (1989)

[文献書誌] H.Kobashi: "Ion-Pair Formation Competing with Internal Conversion from the Second Excited State in the Chloranil-Diphenyl-amine Complex" Chem.Phys.Lett.160. 261-266 (1989)

[文献書誌] T.Kakitani: "Role of Protein Media in the Electron Transfer Reaction" Photosynthetic Research. 22. 187-193 (1989)

[文献書誌] J.D.Batteas: "Photoinduced Charge Separation in a Porphyrin-Tetra-viologen Supramolecular Array" J.Am.Chem.Soc.112. 126-133 (1990)

[文献書誌] H.Miyasaka: "Picosecond Laser Photolysis Studies on the Photoreduction of Excited Benzophenone by Diphenylamine in Solutions" Bull.Chem.Soc.Jpn.63. 131-137 (1990)

[文献書誌] N.Mataga: "Femtosecond-Picosecond Laser Photolysis Studies on the Photoinduced Charge Separation and Charge Recombination of Produced Ion Pair State of Some Typical Intramolecular Exciplex Compounds in Alkanenitrile Solvents" J.Phys.Chem.94. (1990)

[文献書誌] H.Miyasaka: "Picosecond 266 nm Multiphoton Laser Photolysis Studies on Liquid Alkane Solution of Aromatic Hydrocarbons:Ultre-fast Solute Triplet Formation" J.Phys.Chem.64. (1990)

[文献書誌] S.Kinoshita: "Solvent Relaxation Effect on Transient Hole-Burning Spectra of Organic Dyes" Chem.Phys.Lett.(1990)

[文献書誌] A.Harriman: "Photoinduced Intramolecular Electron Transfer in Isomeric Porphyrin-Monoviologen Complexes" J.Phys.Chem.(1990)

[文献書誌] A.Osuka: "Geometry Dependence of Intramolecular Photoinduced Electron Transfer in Synthetic Zinc-Ferric Hybrid Diporphyrins" J.Am.Chem.Soc.

[文献書誌] S.Ojima: "Femtosecond-Picosecond Laser Photolysis Studies on the Dynamics of Excited Charge Transfer Complexes in Solution.II.Ion Pair Formation Processes in the Excited State of 1,2,4,5-Tetracyanobenzene-Aromatic Hydrocarbon Complexes in Polar Solvents" J.Phys.Chem.

[文献書誌] Y.Hirata: "Monophotonic Ionization from the Vibrationally Unrelaxed Excited Singlet State of N,N,N',N'-Tetramethyl-p-pheny-lenediamine in Acetonitrile Solution" J.Phys.Chem.

[文献書誌] Y.Hirata: "Monophotonic Ionization of Benzidine Derivatives in Polar Solvents Studied by Picosecond Transient Absorption Measurements" Chem.Phys.Lett.

[文献書誌] N.Mataga: "Dynamics and Mechanisms of Photoinduced Charge Separation and Charge Recombination of Transient Ion Pair States-Femtosecond〜Picosecond Laser Photolysis Studies" Advances in Chemistry Series,Am.Chem.Soc.“Electron Transfer in Inorganic,Organic and Biological Systems".

[文献書誌] T.Kakitani: "Theoretical Analysis of Energy Gap Laws of Electron Trnasfer Reactions by Considering the Distribution of the Donor and Acceptor Distance" Advances in Chemistry Series,Am.Chem.Soc.“Electron Transfer in Inorganic,Organic and Biological Systems".

[文献書誌] N.Mataga: "Dynamics and Energy Gap Dependences of Photoinduced Charge Separation and Recombination of the Produced Ion Pair State" Photochemical Energy Conversion,Eds.J.R.Norris & D.Meisel,Elsevier. 32-46 (1989)

[文献書誌] N.Mataga: "Excitation Energy Transfer and Photoinduced Electron Transfer Phenomena in Some Confined Systems" Molecular Dynamics in Restricted Geometries,Eds.J.Klafter & J.Drake,John-Wiley. 23-37 (1989)

[文献書誌] F.Tanaka: "Dynamics of Excited State Relaxations in Some Proteins" Photochemistry on Solid Surface,Eds.M.Anpo & T.Matsuura,Elsevier. 551-565 (1989)

[文献書誌] N.Mataga: "Photoinduced Electron Transfer,Electron Photoejection and Related Phenomena in Solutions-Femtosecond〜Nanosecond Laser Photolysis Studies" Advances in Multi-Photon Processes and Spectroscopy,Vol.5,Ed.S.H.Lin,World Scientific. 175-276 (1989)

[文献書誌] 又賀昇: "光電子移動及び関連現象のダイナミックスとメカニズムーフェムト秒、ピコ秒分光による研究" 電気化学および工業物理化学. 57. 1025-1030 (1989)

[文献書誌] H.Miyasaka: "Picosecond Ultraviolet Multiphoton Laser Photolysis Related to Radiolysis" Pulse Radiolysis of Irradiated Systems,Ed.Y.Tabata,CRC.

1989 年度実績報告書

又賀昇大阪大学, 基礎工学部, 教授 (30029368)