1991 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	藤島昭東京大学, 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 / 光合成モデル / 高分散固定化光触媒 / 光情報記録 / レ-ザフラッシュホトリシス / 光化学ホ-ルバ-ニング / 光機能分子
研究概要	有機分子光反応の有機化学及び物理化学的研究の分野ではラジカルカチオンコ-プ転位反応、シリコン誘導体を電子供与体とする電子移動反応、ピラゾリン誘導体の光電子移動反応などのほか光反応によるヒドロキシルラジカルの発生とDNAの選択的切断、半導体レ-ザ-感受性を持つマレイン的無水物に修飾したホトクロミック系化合物の合成等の研究が有機光化学分野で大きな成果を見た。物理光化学の分野ではCIDNPによるチトンαー開裂機構の解明、ポルフィリンーアシトラキノン化合物の光誘起分子内電子移動過程の機構解明、三重項ナフチルアンモニウムイオンからベニゾフェノンへの水素原子移動反応機構解明、低温マトリワクス中での有機スズ化合物光反応機構の解明、極性溶媒体でのエキシプレックス生成による蛍光消光機構の確立、熱レンズ法によるジフェニルアミンのジ〓ドロカルバゾ-ルへの酸化反応熱と三項項エネルギ-の決定、時間分解EPRと光熱分光法を用いたC_<60>,C_<70>の短寿命三重項状態の性質の解明、三重項エネルギ-移動経由の色系増感反応の特異な反応例の研究等で多くの興味ある研究が報告された。超高速分光の分野では直鎖ポリエンの分光と動力学、レンチナ-ル蛋白質の励起状態のフェムト秒分光で極めて興味ある成果を得た。含硫黄メタラサイクル上で起子特異的反応の時間分解ESRによる興味である機構が鎖体系光反応分野から報告された。光化学、電気化学のハイブリット化による光情報記録系の構築は応用面での興味がある成果であった。ラングミュアプロジェット単分子膜における光反応のピコ秒蛍光分光法による研究、ポルフィリン会合体の光誘起電子移動反応の研究は分子系光化学の興味ある研究例であった。研究目的の一つである異なる研究分野の手法の横断的活用の面でも有機光化学の物理光化学間の協同研究が行なわれ、今后の前進が期持される。

研究成果

(30件)

すべてその他

すべて文献書誌 (30件)

[文献書誌] T.Hirano,T.Kumagai,T.Miyashi,K.Akiyama,Y.Ikegami: "Inversion of the Ground State Spin Multiplicity by Electron Withdrawing Groups in Trimethylenemethane Derivatives Generated Photochemically from Methylenequadricyclane Derivatives" J.Org.Chem.,. 57. 876-882 (1992)
[文献書誌] T.Hirano,T.Kumagai,T.Miyashi,K.Akiyama,Y.Ikegami: "Novel Photoreactions of Benzhydrilidenequadricyclane:A New Approach to Trimethylenemethane and Oxyallyl Derivatives" J.Org.Chem.,. 56. 1907-1914 (1991)
[文献書誌] K.KiKuchi,Y.Tkahashi,M.Hoshi,T.niwa,T.Katagiri,T.Miyashi: "Free Enthalpy Dependence of Freeーradical Yield of Photoinduced Electronーtransfer in Acetonitrile" J.Phys.Chem.95. 2378-2381 (1991)
[文献書誌] Kumao.Hamanoue,Toshihiro.Nakyama,Hironobu.Nanshow,Kiminori.Ushida,Yoshinori.Naruta,Toru.Kodo,Kazuhiro.Maruyama: "The excitedーstate dynamics of acetylーand anthraquinoneーlinked α,α,α,αーmesoーtetra(2ーaminophenyl)porphyrin derivatives(XTAPPーAc and XTAPPーAQ)studied by picosecond laser photolysis in acetonitrile at room temperature" Chemical Physics Letters. 187. 409-414 (1991)
[文献書誌] T.Miyashi,Y.Takahashi,H.Ohaku,H.IKeda,and S.Morishima.: "ElectronーTransfer Photoreactions of SmallーRing Compounds.;Nature and Role of Cation Radical Intermediates." Pure and Applied Chemistry(Pure Appl.Chem.). 63. 223-230 (1991)
[文献書誌] T.Sakata,S.Takahashi,M.Terazima,T.Azumi: "Measurement of the Enhancement Factor of Chemically Induced Dynamic Nuclear Polarization in the Photolysis of Dibenzyl Ketone:Determination of the Spin Multiplicity of the Precursor" The Journal of Physical Chemistry. 95. 8671-8676 (1991)
[文献書誌] Y.Hirata and T.Okada: "Vibrational energy dissipation process in solution;picosecond laser photolysis studies of biphenylene" Chem.Phys.Lett.187. 203-207 (1991)
[文献書誌] Isao Saito: "Bis(hydroperoxy)naphthaldiimide as a “PhotoーFenton Reagent":SequenceーSpecific Photocleavage of DNA" Angew.Chem.Int.Ed.Engl.30. 1351-1353 (1992)
[文献書誌] S.Arai,S.Yamauchi,Y.Moriya,T.Tanaka,Y.Yamazaki,H.Inoue,T.Yamagishi,M.Hida: "Synthesis of Naphth(1,2,3ーcd)indolー6(2H)ーnone Derivatives and Their Fluorescence Properties." Bull.Chem.Soc.Jpn.,. 64. 3417-3421 (1991)
[文献書誌] Masakazu ANPO;Masatoshi SUNAMOTO: "Relationship between the Geometry of the Excited State of Vanadium Oxides Auchored onto Sio_2 and Their Photoreactivity toward CO Molecules" Journal of Physical Chemistry. 95. 8813-8818 (1991)
[文献書誌] A.Ogawa,S.Satoh,S.Oh and Y.Shirota: "A Striking Solvent Effect on the Photochemical Reaction of Naphthalene with 2ー(Diethylamino)ethanol" J.Chem.Soc.,Chem.Commun.1195-1196 (1991)
[文献書誌] Shigero OISHI and Takeshi KAWASHIMA: "Photochemical Behavior of Chlorocarbonylbis(triphenylphosphine)rhodium(I),ClRh(CO)P_2 (P=PPh_3).Laser Flash Photolysis with Infrared Detection" Chem.Lett.
[文献書誌] T.Suzuki,Y.Kajii,K.Shibuya,K.Obi: "Calorimetric Standards for Photothermal Methods in Ultraviolet and Visible Spectral Regions" Res.Chem.Intermediates. 15. 261-270 (1991)
[文献書誌] Y.Nakayama,K.Hayashi,M.Irie: "Thermally Irreversible Photochromic Systems.Reversible Photocyclization of NonーSymmetric Diarylethene Derivatives" Bull.Chem.Soc.Japan. 64. 789-795 (1991)
[文献書誌] N.Tamai,H.Matsuo,T.Yamazaki,I.Yamazaki: "Excitation Energy Relaxation of Oxacyanine LangmuirーBlodgett Monolayer Films:Picosecond TimeーResolved Fluorescence Studies" J.Phys.Chem.(1992)
[文献書誌] T.Yamamura,N.Nakamura,A.Yasui,K.Sasaki,and H.Arai: "“Distribution Map of Nickel K‐edge X‐ray Absorption Near Edge Structure.Situation of the Nickels in Hydrogenases in the Map"" Chemistry Letters. 875-878 (1991)
[文献書誌] Ryoichi Akada,Shin Aihara,Hirochika Sakuragi,and Katsumi Tokumaru: "Reactions of 1,1ーDipheny1ー2ーmethylpropene Cation Radicals with Methanol.Ketone Formation Involving Carbocation Rearrangement" Bull.Chem.Soc.Jpn.,. 64. 1419-1421 (1991)
[文献書誌] C.Obayashi,H.Sato,T.Tominaga: "Photochemical Reactions of Tetramethylstannane Isolated in Low Temperature Argon Matrix" J.Radioanal.Nucl.Chem.,Lett.
[文献書誌] Soichiro Kyushin,S.Otani,T.Takahashi,Y.Nakadaira,M.Ohashi: "Photoalkylation of αーDiketones with Tetraalkylstannanes via Electron Transfer" Chemistry Letters. 775-778 (1991)
[文献書誌] A.kato,M.Tono,N.Hisamatsu,S.Nozawa,T.Sugiyama,M.Kajitani,T.Akiyama,A.Sugimori: "Formation of(^<55>ーPentamethylcyclopentadienyl)(lーphenylmethanimineーN,lーdithiolato)cobalt(III)Having a NovelMetallacycle,1,2,5,3ーCobaltadithiazole,in the Reaction of [Co(cp)(CO)_2 with Several Heterocyclic Compounds Containing S and N" Chem.Lett.1992. 243-246 (1992)
[文献書誌] Akira Fujishima: "Second Harmonic Generation Coherent Interferometry Disclosing the Orientation of the Submerged Hemicyanine Layer in a LangmuirーBlodgett Multilayer Structure" J.Phys.Chem.95. 9636-9638 (1991)
[文献書誌] Akira Furusawa,Kazuyuki Horie,Itaru Mita: "LowーTemperature Properties of a Polysilane Studied by Photochemical Hole Burning" J.Molecular Electronics. 7. 69-74 (1991)
[文献書誌] S.Kohno,M.Hoshino and H.Shizuka: "Laser Flash Photolysis Study on the Hydrogen Atom Transfer Reaction from Triplet 2ーNaphthylammonium Ion to Benzophenone.Remarkable Proton Effect" J.Phys.Chem.95. 5489-5495 (1991)
[文献書誌] K.Kikuchi et al.: "Evidence of exciplex formation in acetonitrile" Chem.Phys.Letters. 173. 421-424 (1990)
[文献書誌] Y.Usui,N.Shimizu & S.Mori: "Mechanism on the Ffficient Formation of Singlet Oxygen by Energy Transfer from Excited Singlet and Triplet States of Aromatic Hydrocarbons" Bulletin Chemical Society Japan. 65. (1992)
[文献書誌] T.Minami,N.Tamai,T.Yamazaki,I.Yamazaki: "Picosecond TimeーResolved Fluorescence Spectroscopy of the Photochromic Reaction of Spiropyran in LangmuirーBlodgett Films" J.Phys.Chem.95. 3988-3993 (1991)
[文献書誌] H.Segawa,C.Takehara,K.Honda,T.Shimizu,T.Asahi,N.Mataga: "Photoinduced ElectronーTransfer Reactions of Porphyrin Heteroーaggregates:Energy Gap Dependence of an Intradimer Charge Recombination Process" The Journal of Physical Chemistry. 96. 503-506 (1992)
[文献書誌] Masahde Terazima and Noboru Hirota: "Measurement of the quantum yield of triplet formation and short triplet lifetimes by the transient grating technique" Journal of Chemical Physics. 95. 6490-6495 (1991)
[文献書誌] H.Segawa,C.Takehara,K.Honda,T.Shimidzu,T.Asahi,N.Mataga: "Photoinduced ElectronーTransfar Reactions of Porphyrin Heteroーaggregates:Energy Gap Dependence of an Intradimer Charge Recombination Process" The Journal of Rhysical Chemistry. 96. 503-506 (1992)
[文献書誌] H.Petek,A.J.Bell,K.Yoshihara,R.L.Chrestensen: "Spectroscopic and Dynamical Studies of the S1 and S2 States of Decatetraence in Supersonic Molecular Beams." J.Chem.Phys.,. 95. 4739-4750 (1991)

1991 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] T.Hirano,T.Kumagai,T.Miyashi,K.Akiyama,Y.Ikegami: "Inversion of the Ground State Spin Multiplicity by Electron Withdrawing Groups in Trimethylenemethane Derivatives Generated Photochemically from Methylenequadricyclane Derivatives" J.Org.Chem.,. 57. 876-882 (1992)

[文献書誌] T.Hirano,T.Kumagai,T.Miyashi,K.Akiyama,Y.Ikegami: "Novel Photoreactions of Benzhydrilidenequadricyclane:A New Approach to Trimethylenemethane and Oxyallyl Derivatives" J.Org.Chem.,. 56. 1907-1914 (1991)

[文献書誌] K.KiKuchi,Y.Tkahashi,M.Hoshi,T.niwa,T.Katagiri,T.Miyashi: "Free Enthalpy Dependence of Freeーradical Yield of Photoinduced Electronーtransfer in Acetonitrile" J.Phys.Chem.95. 2378-2381 (1991)

[文献書誌] T.Miyashi,Y.Takahashi,H.Ohaku,H.IKeda,and S.Morishima.: "ElectronーTransfer Photoreactions of SmallーRing Compounds.;Nature and Role of Cation Radical Intermediates." Pure and Applied Chemistry(Pure Appl.Chem.). 63. 223-230 (1991)

[文献書誌] T.Sakata,S.Takahashi,M.Terazima,T.Azumi: "Measurement of the Enhancement Factor of Chemically Induced Dynamic Nuclear Polarization in the Photolysis of Dibenzyl Ketone:Determination of the Spin Multiplicity of the Precursor" The Journal of Physical Chemistry. 95. 8671-8676 (1991)

[文献書誌] Y.Hirata and T.Okada: "Vibrational energy dissipation process in solution;picosecond laser photolysis studies of biphenylene" Chem.Phys.Lett.187. 203-207 (1991)

[文献書誌] Isao Saito: "Bis(hydroperoxy)naphthaldiimide as a “PhotoーFenton Reagent":SequenceーSpecific Photocleavage of DNA" Angew.Chem.Int.Ed.Engl.30. 1351-1353 (1992)

[文献書誌] S.Arai,S.Yamauchi,Y.Moriya,T.Tanaka,Y.Yamazaki,H.Inoue,T.Yamagishi,M.Hida: "Synthesis of Naphth(1,2,3ーcd)indolー6(2H)ーnone Derivatives and Their Fluorescence Properties." Bull.Chem.Soc.Jpn.,. 64. 3417-3421 (1991)

[文献書誌] Masakazu ANPO;Masatoshi SUNAMOTO: "Relationship between the Geometry of the Excited State of Vanadium Oxides Auchored onto Sio_2 and Their Photoreactivity toward CO Molecules" Journal of Physical Chemistry. 95. 8813-8818 (1991)

[文献書誌] A.Ogawa,S.Satoh,S.Oh and Y.Shirota: "A Striking Solvent Effect on the Photochemical Reaction of Naphthalene with 2ー(Diethylamino)ethanol" J.Chem.Soc.,Chem.Commun.1195-1196 (1991)

[文献書誌] Shigero OISHI and Takeshi KAWASHIMA: "Photochemical Behavior of Chlorocarbonylbis(triphenylphosphine)rhodium(I),ClRh(CO)P_2 (P=PPh_3).Laser Flash Photolysis with Infrared Detection" Chem.Lett.

[文献書誌] T.Suzuki,Y.Kajii,K.Shibuya,K.Obi: "Calorimetric Standards for Photothermal Methods in Ultraviolet and Visible Spectral Regions" Res.Chem.Intermediates. 15. 261-270 (1991)

[文献書誌] Y.Nakayama,K.Hayashi,M.Irie: "Thermally Irreversible Photochromic Systems.Reversible Photocyclization of NonーSymmetric Diarylethene Derivatives" Bull.Chem.Soc.Japan. 64. 789-795 (1991)

[文献書誌] N.Tamai,H.Matsuo,T.Yamazaki,I.Yamazaki: "Excitation Energy Relaxation of Oxacyanine LangmuirーBlodgett Monolayer Films:Picosecond TimeーResolved Fluorescence Studies" J.Phys.Chem.(1992)

[文献書誌] T.Yamamura,N.Nakamura,A.Yasui,K.Sasaki,and H.Arai: "“Distribution Map of Nickel K‐edge X‐ray Absorption Near Edge Structure.Situation of the Nickels in Hydrogenases in the Map"" Chemistry Letters. 875-878 (1991)

[文献書誌] Ryoichi Akada,Shin Aihara,Hirochika Sakuragi,and Katsumi Tokumaru: "Reactions of 1,1ーDipheny1ー2ーmethylpropene Cation Radicals with Methanol.Ketone Formation Involving Carbocation Rearrangement" Bull.Chem.Soc.Jpn.,. 64. 1419-1421 (1991)

[文献書誌] C.Obayashi,H.Sato,T.Tominaga: "Photochemical Reactions of Tetramethylstannane Isolated in Low Temperature Argon Matrix" J.Radioanal.Nucl.Chem.,Lett.

[文献書誌] Soichiro Kyushin,S.Otani,T.Takahashi,Y.Nakadaira,M.Ohashi: "Photoalkylation of αーDiketones with Tetraalkylstannanes via Electron Transfer" Chemistry Letters. 775-778 (1991)

[文献書誌] Akira Fujishima: "Second Harmonic Generation Coherent Interferometry Disclosing the Orientation of the Submerged Hemicyanine Layer in a LangmuirーBlodgett Multilayer Structure" J.Phys.Chem.95. 9636-9638 (1991)

[文献書誌] Akira Furusawa,Kazuyuki Horie,Itaru Mita: "LowーTemperature Properties of a Polysilane Studied by Photochemical Hole Burning" J.Molecular Electronics. 7. 69-74 (1991)

[文献書誌] S.Kohno,M.Hoshino and H.Shizuka: "Laser Flash Photolysis Study on the Hydrogen Atom Transfer Reaction from Triplet 2ーNaphthylammonium Ion to Benzophenone.Remarkable Proton Effect" J.Phys.Chem.95. 5489-5495 (1991)

[文献書誌] K.Kikuchi et al.: "Evidence of exciplex formation in acetonitrile" Chem.Phys.Letters. 173. 421-424 (1990)

[文献書誌] Y.Usui,N.Shimizu & S.Mori: "Mechanism on the Ffficient Formation of Singlet Oxygen by Energy Transfer from Excited Singlet and Triplet States of Aromatic Hydrocarbons" Bulletin Chemical Society Japan. 65. (1992)

[文献書誌] T.Minami,N.Tamai,T.Yamazaki,I.Yamazaki: "Picosecond TimeーResolved Fluorescence Spectroscopy of the Photochromic Reaction of Spiropyran in LangmuirーBlodgett Films" J.Phys.Chem.95. 3988-3993 (1991)

[文献書誌] H.Segawa,C.Takehara,K.Honda,T.Shimizu,T.Asahi,N.Mataga: "Photoinduced ElectronーTransfer Reactions of Porphyrin Heteroーaggregates:Energy Gap Dependence of an Intradimer Charge Recombination Process" The Journal of Physical Chemistry. 96. 503-506 (1992)

[文献書誌] Masahde Terazima and Noboru Hirota: "Measurement of the quantum yield of triplet formation and short triplet lifetimes by the transient grating technique" Journal of Chemical Physics. 95. 6490-6495 (1991)

[文献書誌] H.Segawa,C.Takehara,K.Honda,T.Shimidzu,T.Asahi,N.Mataga: "Photoinduced ElectronーTransfar Reactions of Porphyrin Heteroーaggregates:Energy Gap Dependence of an Intradimer Charge Recombination Process" The Journal of Rhysical Chemistry. 96. 503-506 (1992)

[文献書誌] H.Petek,A.J.Bell,K.Yoshihara,R.L.Chrestensen: "Spectroscopic and Dynamical Studies of the S1 and S2 States of Decatetraence in Supersonic Molecular Beams." J.Chem.Phys.,. 95. 4739-4750 (1991)

1991 年度実績報告書

宮仕勉東北大学, 理学部, 教授 (20004442)