1993 年度実績報告書

分子および分子系の光化学の新展開

研究課題

研究課題/領域番号	03303001
研究機関	東北大学
研究代表者	宮仕勉東北大学, 理学部, 教授 (20004442)
研究分担者	藤嶋昭東京大学, 工学部, 教授 (30078307) 斉藤烈京都大学, 工学部, 教授 (20026082) 閑春夫群馬大学, 工学部, 教授 (40008454) 小尾欣一東京工業大学, 理学部, 教授 (10016090) 入江正浩九州大学, 機能物質科学研究所, 教授 (30001986)
キーワード	光誘起電子移動反応 / ゼオライト光触媒 / 金属・分子クラスター / フォトクロミズム / 光フェントン試薬 / レーザー光分解 / 光化学反応 / 光機能材料
研究概要	有機分子の有機・物理化学的及び放射線励起の研究では、フラッシュホトリシスよるケトン誘導体の炭素-炭素結合開裂反応速度の初めての測定、光電子移動Cope転位反応機構の確立、応用の期待される新規フォトクロミック分子の合成と光反応、励起光より高エネルギーで起こる増感p型一重項反応機構の確立、光励起と電子線励起で生ずるイオンラジカルの反応性の相違の詳細な検討、TMMビラジカルの新規発生法、電子移動消光に関するRehm-Weller式の新解釈法の確立、アゾ化合物の特異的光電子移動反応の発見、環状ケトンからの三重項ビラジカル動的反応挙動の解析、三重項錯体経由の水素原子移動反応機構と錯体構造の決定、電子移動で生ずるイオン対と遊離イオンの反応特性の相違、アントラキノン誘導体の分子内・分子間水素引抜き反応機構の確立、エンドペルオキシドの電子移動逆Diels-Alder反応の発見等で大きな成果を得た。また有機と物理化学者間での協同研究が活発に進められた。無機系及び生体関連光反応分野では、高原子価金属ポルフィリンと水を用いた光電子移動によるオレフィンのエポキシ化、時間分解赤外分光による不安定金属中間体の構造研究、質量選別多光子イオン化分光による金属・分子クラスターの生成と反応性、光反応による含硫黄有機金属-メタラジチオレンラジカルの特異的反応、メスバウアー分光法による有機金属化合物の光反応の解析、光機能材料の光界面効果、ペプチドポルフィリンの光反応、応用の期待できるDNA切断光フェントン試薬の開発等注目すべき結果を得た。分子系の分野では、環境化学でも注目される銅イオン-ゼオライト光触媒によるのNOx分解反応、含ポルフィリンポリマーの光電変換素子への応用、新しい二波長光増感型光化学ホールバーニングの発見、芳香族炭化水素系LB膜中有機分子の光化学挙動の研究等で大きな成果を得た。超高速分光・磁気共鳴分野では、CIDNP増大因子と光反応機構の関係、アントリレンオリゴマーの光誘起電荷分離機構、時間分解EPRによるC60,C70分子の励起状態の研究、超高速レーザー分光による溶媒和過程より早い新型電子移動の観測等で有機光化学的にも興味ある事実が数多く見出された。

研究成果
(29件)

すべてその他

すべて文献書誌 (29件)

[文献書誌] R.Akaba: "Photoinduced Electron Transfer Reactions of Di(4-methoxyphenyl)ethanol in Solution.Sensitizer-dependent Decay Pathways of the Aldehyde Cation Radical" Chem.Lett.1157-1160 (1993)
[文献書誌] H.Ikeda: "The Cation-Radical Cope Rearrangement of 2,5-Diphenylhexa-1,5-dienes under Electron" J.Chem.Soc.,Chem.Commun.367-369 (1993)
[文献書誌] M.Irie: "Photochromic Diarylethenes for Optical Data Storage Media"" Mol.Cryst.Liq.Cryst.227. 263-270 (1993)
[文献書誌] Y.Usui: "Photochemical Nitration of Benzoic Acid Derivatives by Irradiation to Nitrate Ions" Bull.Chem.Soc.Jpn.66. 3182-3185 (1993)
[文献書誌] T.Kinumi: "The Conformational Analysis and Photoisomerization of Retinochrome Analogs with Polyenals" J.Photochem.Photobiol.58. 409-412 (1993)
[文献書誌] K.Kikuchi: "New Aspects on Fluorescence Quenching by Molecular Oxygen" J.Am.Chem.Soc.115. 5180-5184 (1993)
[文献書誌] H.Itih: "Steric Effects in Photochemical Cycloadditions of 9-Phenanthrenecarboxylates" Bull.Chem.Soc.Jpn.66. 340-343 (1993)
[文献書誌] T.Sekiguch: "Laser Flash Photolysis Studies on Intramolecular Hydrogen Atom Transfer of[(Hydroxynaphtyl)propyl]benzophenone and Intramolecular Proton-Induced Electron Transfer of [(Methoxynaphtyl)propyl]benzophenone via Triplet Exciplexes" J.Phys.Chem.97. 7003-7010 (1993)
[文献書誌] A.Wakisaka: "The Simplest Process in the Growth Carbon Clusters:C_2 Formation from C_1 following Laser Vaporization of Graphite" J.Chem.Soc.,Chem.Commun.77-78 (1993)
[文献書誌] Y.Kuriyama: "Mechanism for Isomerization of Cis-stilbene via Its Radical Cation as Investigated by Pulse Radiolysis.A Possible Role of a Dimeric Radical Cation as an Intermediate" Bull.Chem.Soc.Jpn.66. 1852-1855 (1993)
[文献書誌] T.Nakayama: "Intra-and Inter-molecular Hydrogen-atom Abstraction of Photoexcited 1,4-Dimethylanthraquinone" Chem.Phys.Lett.213. 581-585 (1993)
[文献書誌] H.Ikeda: "Striking Contrast between Photoinduced and Non-photoinduced Electron-transfer Reactions of 1,4-Diphenyl-2,3-diazabicyclo[2.2.2]oct-2-ene" J.Chem.Soc.,Chem.Commun.(in press).
[文献書誌] S.Takagi: "Photochemical Electron Transfer from Hydroxide Ion to the Excited Triplet State of Tetraphenyl-porphyrinatoantimony(V)upon Visible Light Irradiation in Aqueous Acetonitrile" Chem.Lett.793-796 (1993)
[文献書誌] S.Oishi: "Structure of Transient Cr(CO)_5(phen)Studied by Time-resolved Infrared Spectroscopy" Chem.Lett.713-716 (1993)
[文献書誌] A.Nakajima: "Electronic Shell Structure of Indium-Sodium(InnNam)Bimetallic Clusters Examined by Ionization Potentials and Mass Distributions" J.Phys.Chem.97. 86-90 (1993)
[文献書誌] T.Morii: "Sequence-Specific DNA Binding by a Geometrically Constrained Peptide Dimer" J.Am.Chem.Soc.115. 1150-1151 (1993)
[文献書誌] S.Yamauchi: "Photolysis and Pyrolysis of Europium Compounds in Solid and Frozen Solution System:Mossbauer and ESR Study" Radiochimica.Acta.115. 1150-1151 (1993)
[文献書誌] A.Fujishima: "Biochemical Application of Photoelectrochemistry Photokilling of Malignant Cells with TiO2 Powder" Electrochimica.Acta.18. 153-157 (1993)
[文献書誌] T.Yamamura: "A Square Planar NiS4 Unit with an Aliphatic Thiolato-Thioether Donor Set:A Carbon Monoxide Dehydrogenase Model Binds CO" J.Chem.Soc.,Chem.Commun.(in press).
[文献書誌] M.Anpo: "Intrinsic Surface Structure and Their Role in the Catalysis and Photocatalysis of Microcrystalline MgO Catalysis" Res.Chem.Intermedi.19. 495-521 (1993)
[文献書誌] H.Segawa: "One-Dimensional Donor-Acceptor Polymer:Phosphorus Porphyrins Linked with Molecular Wire" Synth.Metal.55-57. 966-971 (1993)
[文献書誌] K.Nishimura: "Hole Drift Mobilities in the Glassy State of Arylaldehyde and Arylketone Hydrazones" Mol.Cryst.Liq.Cryst.217. 235-242 (1993)
[文献書誌] S.Machida: "Enhancement of Non-Photochemical Hole Burning by Two-Color Excitation in Polymers Containing Carboxylic Acid" J.Phys.Chem.97. 8234-8239 (1993)
[文献書誌] N.Mataga: "Geometry-and Solvent-Polarity Dependent Photoinduced Electron Transfer in Conformationally Restricted Magnesium-free-base hybrid Diporphyrins" Chem.Phys.Lett.201. 223-228 (1993)
[文献書誌] Q.Meng: "Triplet Mechanism of CIDNP in the Photolysis of Benzoquinones As Studied by Dynamic Nuclear Polarization" J.Phys.Chem.97. 1265-1269 (1993)
[文献書誌] Y.Hirata: "Higher Excited Singlet State of Diphenylacetylene in Solution Phase" Chem.Phys.Lett.209. 397-402 (1993)
[文献書誌] T.Ishiwata: "Optical-Optical Double Resonance Spectroscopy of the I_2l_g(^1D)Ion-Pair State" J.Mol.Spectrosc.159. 443-475 (1993)
[文献書誌] N.Hoshi: "Pressure Effect on the Photoinduced Hydrogen Abstraction Reactions of Azanaphthalenes in Mixed Crystals of Durene" J.Phys.Chem.95. 2146-2150 (1993)
[文献書誌] A.Yartsev: "Solvent and Nuclear Dynamics in Ultrafast Intermolecular Electron Transfer in a Diffusionless,Weakly Polar System" Chem.Phys.Lett.207. 546-550 (1993)

1993 年度 実績報告書

分子および分子系の光化学の新展開

研究代表者

宮仕 勉 東北大学, 理学部, 教授 (20004442)

研究成果

[文献書誌] R.Akaba: "Photoinduced Electron Transfer Reactions of Di(4-methoxyphenyl)ethanol in Solution.Sensitizer-dependent Decay Pathways of the Aldehyde Cation Radical" Chem.Lett.1157-1160 (1993)

[文献書誌] H.Ikeda: "The Cation-Radical Cope Rearrangement of 2,5-Diphenylhexa-1,5-dienes under Electron" J.Chem.Soc.,Chem.Commun.367-369 (1993)

[文献書誌] M.Irie: "Photochromic Diarylethenes for Optical Data Storage Media"" Mol.Cryst.Liq.Cryst.227. 263-270 (1993)

[文献書誌] Y.Usui: "Photochemical Nitration of Benzoic Acid Derivatives by Irradiation to Nitrate Ions" Bull.Chem.Soc.Jpn.66. 3182-3185 (1993)

[文献書誌] T.Kinumi: "The Conformational Analysis and Photoisomerization of Retinochrome Analogs with Polyenals" J.Photochem.Photobiol.58. 409-412 (1993)

[文献書誌] K.Kikuchi: "New Aspects on Fluorescence Quenching by Molecular Oxygen" J.Am.Chem.Soc.115. 5180-5184 (1993)

[文献書誌] H.Itih: "Steric Effects in Photochemical Cycloadditions of 9-Phenanthrenecarboxylates" Bull.Chem.Soc.Jpn.66. 340-343 (1993)

[文献書誌] T.Sekiguch: "Laser Flash Photolysis Studies on Intramolecular Hydrogen Atom Transfer of[(Hydroxynaphtyl)propyl]benzophenone and Intramolecular Proton-Induced Electron Transfer of [(Methoxynaphtyl)propyl]benzophenone via Triplet Exciplexes" J.Phys.Chem.97. 7003-7010 (1993)

[文献書誌] A.Wakisaka: "The Simplest Process in the Growth Carbon Clusters:C_2 Formation from C_1 following Laser Vaporization of Graphite" J.Chem.Soc.,Chem.Commun.77-78 (1993)

[文献書誌] Y.Kuriyama: "Mechanism for Isomerization of Cis-stilbene via Its Radical Cation as Investigated by Pulse Radiolysis.A Possible Role of a Dimeric Radical Cation as an Intermediate" Bull.Chem.Soc.Jpn.66. 1852-1855 (1993)

[文献書誌] T.Nakayama: "Intra-and Inter-molecular Hydrogen-atom Abstraction of Photoexcited 1,4-Dimethylanthraquinone" Chem.Phys.Lett.213. 581-585 (1993)

[文献書誌] H.Ikeda: "Striking Contrast between Photoinduced and Non-photoinduced Electron-transfer Reactions of 1,4-Diphenyl-2,3-diazabicyclo[2.2.2]oct-2-ene" J.Chem.Soc.,Chem.Commun.(in press).

[文献書誌] S.Takagi: "Photochemical Electron Transfer from Hydroxide Ion to the Excited Triplet State of Tetraphenyl-porphyrinatoantimony(V)upon Visible Light Irradiation in Aqueous Acetonitrile" Chem.Lett.793-796 (1993)

[文献書誌] S.Oishi: "Structure of Transient Cr(CO)_5(phen)Studied by Time-resolved Infrared Spectroscopy" Chem.Lett.713-716 (1993)

[文献書誌] A.Nakajima: "Electronic Shell Structure of Indium-Sodium(InnNam)Bimetallic Clusters Examined by Ionization Potentials and Mass Distributions" J.Phys.Chem.97. 86-90 (1993)

[文献書誌] T.Morii: "Sequence-Specific DNA Binding by a Geometrically Constrained Peptide Dimer" J.Am.Chem.Soc.115. 1150-1151 (1993)

[文献書誌] S.Yamauchi: "Photolysis and Pyrolysis of Europium Compounds in Solid and Frozen Solution System:Mossbauer and ESR Study" Radiochimica.Acta.115. 1150-1151 (1993)

[文献書誌] A.Fujishima: "Biochemical Application of Photoelectrochemistry Photokilling of Malignant Cells with TiO2 Powder" Electrochimica.Acta.18. 153-157 (1993)

[文献書誌] T.Yamamura: "A Square Planar NiS4 Unit with an Aliphatic Thiolato-Thioether Donor Set:A Carbon Monoxide Dehydrogenase Model Binds CO" J.Chem.Soc.,Chem.Commun.(in press).

[文献書誌] M.Anpo: "Intrinsic Surface Structure and Their Role in the Catalysis and Photocatalysis of Microcrystalline MgO Catalysis" Res.Chem.Intermedi.19. 495-521 (1993)

[文献書誌] H.Segawa: "One-Dimensional Donor-Acceptor Polymer:Phosphorus Porphyrins Linked with Molecular Wire" Synth.Metal.55-57. 966-971 (1993)

[文献書誌] K.Nishimura: "Hole Drift Mobilities in the Glassy State of Arylaldehyde and Arylketone Hydrazones" Mol.Cryst.Liq.Cryst.217. 235-242 (1993)

[文献書誌] S.Machida: "Enhancement of Non-Photochemical Hole Burning by Two-Color Excitation in Polymers Containing Carboxylic Acid" J.Phys.Chem.97. 8234-8239 (1993)

[文献書誌] N.Mataga: "Geometry-and Solvent-Polarity Dependent Photoinduced Electron Transfer in Conformationally Restricted Magnesium-free-base hybrid Diporphyrins" Chem.Phys.Lett.201. 223-228 (1993)

[文献書誌] Q.Meng: "Triplet Mechanism of CIDNP in the Photolysis of Benzoquinones As Studied by Dynamic Nuclear Polarization" J.Phys.Chem.97. 1265-1269 (1993)

[文献書誌] Y.Hirata: "Higher Excited Singlet State of Diphenylacetylene in Solution Phase" Chem.Phys.Lett.209. 397-402 (1993)

[文献書誌] T.Ishiwata: "Optical-Optical Double Resonance Spectroscopy of the I_2l_g(^1D)Ion-Pair State" J.Mol.Spectrosc.159. 443-475 (1993)

[文献書誌] N.Hoshi: "Pressure Effect on the Photoinduced Hydrogen Abstraction Reactions of Azanaphthalenes in Mixed Crystals of Durene" J.Phys.Chem.95. 2146-2150 (1993)

[文献書誌] A.Yartsev: "Solvent and Nuclear Dynamics in Ultrafast Intermolecular Electron Transfer in a Diffusionless,Weakly Polar System" Chem.Phys.Lett.207. 546-550 (1993)

1993 年度実績報告書

宮仕勉東北大学, 理学部, 教授 (20004442)