1994 Fiscal Year Annual Research Report

凝縮相における光反応ダイナミックス

Research Project

Project/Area Number	06239101
Research Institution	Gunma University
Principal Investigator	閑春夫群馬大学, 工学部, 教授 (40008454)
Co-Investigator(Kenkyū-buntansha)	小山泰関西学院大学, 理学部, 教授 (90079666) 増原宏大阪大学, 工学部, 教授 (60029551) 大野健大阪大学, 理学部, 教授 (10029697) 濱之上熊男京都工芸繊維大学, 工芸学部, 教授 (30025374)
Keywords	レーザー光分解法 / 電子移動 / 水素原子移動 / 光異性化反応 / アブレ-ジョン / ナノ秒画像解析法 / ナノ秒写真観測法 / 励起状態
Research Abstract	種々の凝縮系環境場において、ナノ秒・ピコ秒光分解法及びラマン分解法を用いた動的解析により、凝縮系における光反応ダイナミックスの解明に以下の様な成果を得た。 (1)励起有機分子の凝縮相における光過程(群馬大・工・閑春夫)三重項ベンゾフェノンからナフタレン誘導体へのエネルギー移動はDexter理論の予測とは異なり、極性溶媒の方がエネルギー移動速度が大きく拡散律速に近いこと、またエネルギー移動後の水素原子移動やプロトン誘起電子移動反応がゆるいサンドイッチ型の弱い電荷移動構造をもつ三重項錯体内で起こることを明らかにした。 (2)凝縮相における高励起状態反応ダイナミックス(京都工繊大・工芸・濱之上熊男)分子構造的に大きな歪みを有するシクロファンアントラキノンのベンゼン中における光化学過程を検討し、励起一重項状態からは一重項ビラジカルの生成と項間交差により三重項状態を経由する三重項ビラジカルの生成過程を溶媒効果及び励起エネルギー効果の点から明らかにした。 (3)界面における動的分子間相互作用(阪大・工・増原宏)ピコ秒正反射分光法、ナノ秒干渉画像計測法及び写真観測法を開発し、有機分子固体表面層の高速光熱変換過程・膨張・収縮ダイナミックス、爆蝕プロセス、さらに界面の電子移動過程を直接測定することに成功した。 (4)固溶体における光電子移動反応(阪大・理・大野健)固溶体のRuL_3X_2錯塩結晶の電荷移動燐光状態は、(a)溶媒和水による無輻射失活を受ける(b)励起マイグレーションは遅い(c)水和イオン対結晶における電子移動において溶媒和水分子の再配列は無視てきることを明らかにした。 (5)時間分解ラマン分光法による光合成初期過程の研究(関西学院大・理・小山泰)光反応中心に結合したスフェロインデンの過渡ラマンスペクトルを測定し、T_1状態のC_<15>=C_<15>'のかたまりのねじれと15シスから全トランスへの異性化を見出した。また、レチナ-ルのT_1ラマンスペクトルから、共役系の結合次数を決定した。

Research Products
(35 results)

All Other

All Publications (35 results)

[Publications] T.Nakayama, S.Miki, F.M.Abdel-Latif, K.Lbuki, and K.Hamanoue: "Spectroscopic Study of the Formation and Decay of Intermediates for the Novel Photochemistry of Sterically Strained[6]-1,4-cyclophane-anthraquinone." Chem.Phys.Lett.220. 219-224 (1994)
[Publications] T.Nakayama, A.Otani, and K.Hamanoue: "Effects of Water on the Phosphorescence Spectra of Aromatic Carbonyl Compounds. Part 3.-Dual or Multiple-component Phosphorescence of 1-Indanone at 77K in Some Protic Solvents containing Water." J.Chem.Soc.Faraday Trans.91(in press). (1995)
[Publications] T.Nakayama, N.Nakamura, S.Miki, and K.Hamanoue: "Formation of Anthrahydroquinones(XAQH_2) via Excited Singlet Charge-Transfer Complexes (or Singlet Ion Pairs) of Anthraquinones with 2,5-Dimethylhexa-2,4-diene(DMHD), and Photochemical Rection of XAQH2 with DMHD." J.Chem.Soc.Faraday Trans.91(in press). (1995)
[Publications] K.Hamanoue, T.Nakayama, I.Tsujimoto, S.Miki, and K.Ushida: "Further Studies on the Nature of the Lowest Excited Triplet State of Haloanthraquinones: Triplet-Triplet Absorption and Phosphorescence Spectra of α -halo(1-bromo, 1-bromo-5-chloro, 1,5-dibromo, 1-bromo-8-chloro and 1,8-dibromo) and β -halo(2-bromo)Compounds." J.Phys.Chem.99(in press). (1995)
[Publications] R.Arakawa, T.Matsuo, H.Ito, I.Katakuse, K.Nozaki, T.Ohno, and M.Haga: "Multiply Charged Ion of Ruthenium(II), Rhodium(III) and Cobalt(III) Complexes in Electrospray Ionization Mass Spectroscopy." Org.Mass Spectr.29. 289-294 (1994)
[Publications] M.Haga, T.Ano, T.Ishizaki, K.Kano, K.Nozaki, and T.Ohno: "Synthesis and Proton-Coupled Redox Properties of Mononuclear or Asymmetric Dinuclearcomplexes of Ruthenium, Rhodium and/or Osmium Containing 2,2'-bis(2-pyridyl)-6,6'-bibensimidazole." J.Chem.Soc.Dalton Trans.263-272 (1994)
[Publications] T.Nakayama, S.Miki, F.M.Abdel-Latif, K.Lbuki, and K.Hamanoue: "Spectroscopic Study of the Formation and Decay of Intermediates for the Novel Photochemistry of Sterically Strained[6]1,4-cyclophane-anthraquinone." Chem.Phys.Lett.220. 219-224 (1994)
[Publications] T.Nakayama, A.Otani, and K.Hamanoue: "Effects of Water on the Phosphorescence Spectra of Aromatic Carbonyl Compounds. Part3.-Dual or Multiple-component Phosphorescence of 1-Indanone at 77K in Some Protic Solvents containing Water." J.Chem.Soc.Faraday Trans.91(in press). (1995)
[Publications] T.Nakayama, N.Nakamura, S.Miki, and K.Hamanoue: "Formation of Anthrahydroquinones(XAQH_2)via Excited Singlet Charge-Transfer Complexes(or Singlet Ion Pairs) of Anthraquinones with 2,5-Dimethylhexa-2,4-diene(DMHD), and Photochemical Rection of XAQH2 with DMHD." J.Chem.Soc.Faraday Trans.91(in press). (1995)
[Publications] K.Hamanoue, T.Nakayama, I.Tsujimoto, S.Miki, and K.Ushida: "Further Studies on the Nature of the Lowest Excited Triplet State of Haloanthraquinones: Triplet -Triplet Absorption and Phosphorescence Spectra of α -halo(1-bromo, 1-bromo-5-chloro, 1,5-dibromo, 1-bromo-8-chloro and 1,8-dibromo) and β -halo(2-bromo) Compounds." J.Phys.Chem.99(in press). (1995)
[Publications] R.Arakawa, T.Matsuo, H.Ito, I.Katakuse, K.Nozaki, T.Ohno, and M.Haga: "Multiply Charged Ion of Ruthenium(II), Rhodium(III) and Cobalt(III) Complexes in Electrospray Ionization Mass Spectroscopy." Org.Mass Spectr.29. 289-294 (1994)
[Publications] M.Hage, T.Ano, T.Ishizaki, K.Kano, K.Nozaki, and T.Ohno: "Synthesis and Proton-Coupled Redox Properties of Mononuclear or Asymmetric Dinuclearcomplexes of Ruthenium, Rhodium and/or Osmium Containing 2,2'-bis(2-pyridyI)-6,6'-bibensimidazole." J.Chem.Soc.Dalton Trans.263-272 (1994)
[Publications] T.Ohno, K.Nozaki, A.Yoshimura, N.Ikeda, and T.Iguro: "Photoinduced Intramolecular Electron Transfer Reactions within donoracceptor Linkedcompounds in Solution and within Donor-Acceptor Ion-Pairs in Crystal" Res.Chem.Intermed.20. 807-814 (1994)
[Publications] M.Haga, M.M.Ali, S.Koseki, A.Yoshimura, K.Nozaki, and T.Ohno: "Synthesis, Electrochemistry and Photoexcited-State Properties of Dinuclear Rutheniumcomplexes Bridged by 2,6'-bis(2-pyridyl)-2,2':6,2"-thiazolo-[4,5-d]-benzothiazole." Inorg.Chim.Acta. 226. 17-24 (1994)
[Publications] T.Iguro, N.Ikeda, and T.Ohno: "Electron Transfer Quenching of the Excited MLCT State of Ru(II) in the Double Complex Salts[Ru(bpy)_3]_2[M(CN)_6]Cl・8H_2O(M=Co and Fe)." Inorg.chim.Acta. 226. 203-211 (1994)
[Publications] N.Fukazawa, H.Fukumura, H.Masuhara and J.Prochorow: "A Picosecond Diffuse Reflectance Laser Photolysis Study on Phenanthrene-Pyromellitic Dianhydride Charge-Transfer Crystal." Chem.Phys.Lett.220. 461-466 (1994)
[Publications] H.Fukumura and H.Masuhara: "The Mechanism of Dopant-Induced Laser Ablation. Possibility of Cyclic Multiphotonic Absorption in Excited States." Chem.Phys.Lett.221. 373-378 (1994)
[Publications] N.Fukazawa, H.Fukumura, and H.Masuhara: "Picosecond Diffuse Reflectance Laser Photolysis Study on 9,10-dichloroanthracene and 9,10-dibromoanthracene microcrystals" Chem.Phys.Lett.222. 123-128 (1994)
[Publications] H.Furutani, H.Fukumura, and H.Masuhara: "A.Nanosecond Time-Resolved Interferometric Study on Morphological Dytamics of Doped Poly(Methyl Methacrylare) Film upon Laser Ablation." Appl.Phys.Lett.65. 3413-3415 (1994)
[Publications] T.Ueda, R.Fujisawa, H.Fukumura, A.Itaya, and H.Masuhara: "Electronic Structure and Dynamics of Ionic Species in Thin Poly(N-Vinylcarbazole) Films Doped with Some Electron Acceptors as Revealed by Transient Absorption Spectroscopy." J.Phys.Chem.(in press). (1995)
[Publications] H.Fukumura, E.Takahashi, and H.Masuhara: "Time-Resolved Spectroscopic and Photographic Studies on Laser Ablation Mechanism of Doped Poly(Mathyl Metacrylate) Film" J.Phys.Chem.(in press). (1995)
[Publications] K.Watanabe, T.Asahi, and H.Masuhara: "Hole Diffusion-Controlled Geminate Charge Recombination Dynamics in Doped Poly(N-Vinylcarbazole) Films by Transient Absorption Spectroscopy." Chem.Phys.Lett.(in press). (1995)
[Publications] M.Kuki, H.Nagae, R.J.Cogdell, K.Shimada, and Y.Koyama: "Solvent Effect on Spheroidene Nonpolar and Polar Solutions and the Environments of Spheroidene in the Light-Harvesting Complexes of Rhodobacter sphaeroides 2.4.1 as Revealed by the Energy of the ^1Ag^-→^1Bu^+ Absorption and the Frequencies of the Vibronically Coupled C=C Stretching Raman Lines in the ^1Ag^- and 2 ^1Ag^- States." Photochem.Photobiol.59. 116-124 (1994)
[Publications] H.Fujiwara, T.Hayashi, H.Fukumura, and H.Masuhara: "Each Dopant can Absorb More than Ten Photons: Transient Absorbance Measurement at Excitation Laser Wavelength in Polymer Ablation." Appl.Phys.Lett.64. 2451-2453 (1994)
[Publications] Y.Tsuboi, H.Fukumura, and H.Masuhara: "Nanosecond Imaging Study on Laser Ablation of Liquid Benzene." Appl.Phys.Lett.64. 2745-2747 (1994)
[Publications] S.Hashimoto, N.Fukazawa, H.Fukumura, and H.Masuhara: "Diffuse Reflectance Laser Photolysis Study on Triplet Complex between Aromatics and T1+lncluded in TI-exchanged X-Type Zeolite." Chem.Phys.Lett.223. 493-500 (1994)
[Publications] H.Fukumura, Y.Kohji, K.Nagasawa, and H.Masuhara: "Laser Implantation of Pyrene Molecules into Poly(methyl Methacrylate) Films." J.Am.Chem.Soc.116. 10304-10305 (1994)
[Publications] Y.Tsuboi, K.Hatanaka, H.Fukumura, and H.Masuhara: "248nm Excimer Laser Ablation of Liquid Benzene Derivatives: A Relation between Ablation Threshold and Molecular Photochemical Reactivity." J.Phys.Chem.98. 11237-11241 (1994)
[Publications] M.Ichikawa, H.Fukumura, and H.Masuhara: "Picosecond Regular Reflection Spectroscopic Study on Ultrafast Photoinduced Heat Generation in Copper Phthanlocyanine Solid." J.Phys.Chem.98. 12211-12214 (1994)
[Publications] E.Nishizawa, L.Limantara, N.Nanjou, H.Nagae, T.Kakuno, and K.Koyama: "Solvent Effect on Triplet-State Bacteriochlorophyll a as Detected by Transient Raman Spectroscopy and the Environment of Bacteriochlorophyll a in the Light-Harvesting Complex of Rhodobacter sphaeroides R26." Photochem.Photobiol.59. 229-236 (1994)
[Publications] H.Nakagawa, Y.Koyama, and T.Okada: "Cytochrome c Electronic Structure Characterization toward the Analysis of Electron Transfer Mechanism." J.Biochem.115. 891-897 (1994)
[Publications] V.F.Kamalov, I.A.Struganova, Y.Koyama, and K.Yoshihara: "Two-Exciton Emission of BICJ-Aggregates" Chem.Phys.Lett.226. 132-136 (1994)
[Publications] L.Limantara, Y.Koyama, I.Katheder, and H.Scheer: "Transient Raman Spectroscopy of 15N-Substituted Bacteriochlorophyll a.An Empirical Assignment of T1 Raman Lines." Chem.Phys.Lett.227. 617-622 (1994)
[Publications] H.Nagae, M.Kuki, R.J.Cogdell, and Y.Koyama: "Shifts of the ^1Ag^-→^1Bu^+ Electronic Absorption of Carotenoids in Nonpolar and Polar Solvents." J.Chem.Phys.101. 6750-6765 (1994)
[Publications] E.Nishizawa, N.Nagae, and Y.Koyama: "Transient Absorption Spectroscopy of Bacteriochlorophyll a:Cation Radical Generated in Solvents Forming Aggregates and T1 Species Generated in Solvents Forming Aggregates and T1 Species Generated in Solvents Forming Penta- and Hexacoordinated Monomers with and without Hydrogen Bonding." J.Phys.Chem.98. 12086-12090 (1994)

1994 Fiscal Year Annual Research Report

凝縮相における光反応ダイナミックス

Principal Investigator

閑 春夫 群馬大学, 工学部, 教授 (40008454)

Research Products

[Publications] T.Nakayama, S.Miki, F.M.Abdel-Latif, K.Lbuki, and K.Hamanoue: "Spectroscopic Study of the Formation and Decay of Intermediates for the Novel Photochemistry of Sterically Strained[6]-1,4-cyclophane-anthraquinone." Chem.Phys.Lett.220. 219-224 (1994)

[Publications] T.Nakayama, A.Otani, and K.Hamanoue: "Effects of Water on the Phosphorescence Spectra of Aromatic Carbonyl Compounds. Part 3.-Dual or Multiple-component Phosphorescence of 1-Indanone at 77K in Some Protic Solvents containing Water." J.Chem.Soc.Faraday Trans.91(in press). (1995)

[Publications] R.Arakawa, T.Matsuo, H.Ito, I.Katakuse, K.Nozaki, T.Ohno, and M.Haga: "Multiply Charged Ion of Ruthenium(II), Rhodium(III) and Cobalt(III) Complexes in Electrospray Ionization Mass Spectroscopy." Org.Mass Spectr.29. 289-294 (1994)

[Publications] M.Haga, T.Ano, T.Ishizaki, K.Kano, K.Nozaki, and T.Ohno: "Synthesis and Proton-Coupled Redox Properties of Mononuclear or Asymmetric Dinuclearcomplexes of Ruthenium, Rhodium and/or Osmium Containing 2,2'-bis(2-pyridyl)-6,6'-bibensimidazole." J.Chem.Soc.Dalton Trans.263-272 (1994)

[Publications] T.Nakayama, S.Miki, F.M.Abdel-Latif, K.Lbuki, and K.Hamanoue: "Spectroscopic Study of the Formation and Decay of Intermediates for the Novel Photochemistry of Sterically Strained[6]1,4-cyclophane-anthraquinone." Chem.Phys.Lett.220. 219-224 (1994)

[Publications] T.Nakayama, A.Otani, and K.Hamanoue: "Effects of Water on the Phosphorescence Spectra of Aromatic Carbonyl Compounds. Part3.-Dual or Multiple-component Phosphorescence of 1-Indanone at 77K in Some Protic Solvents containing Water." J.Chem.Soc.Faraday Trans.91(in press). (1995)

[Publications] R.Arakawa, T.Matsuo, H.Ito, I.Katakuse, K.Nozaki, T.Ohno, and M.Haga: "Multiply Charged Ion of Ruthenium(II), Rhodium(III) and Cobalt(III) Complexes in Electrospray Ionization Mass Spectroscopy." Org.Mass Spectr.29. 289-294 (1994)

[Publications] M.Hage, T.Ano, T.Ishizaki, K.Kano, K.Nozaki, and T.Ohno: "Synthesis and Proton-Coupled Redox Properties of Mononuclear or Asymmetric Dinuclearcomplexes of Ruthenium, Rhodium and/or Osmium Containing 2,2'-bis(2-pyridyI)-6,6'-bibensimidazole." J.Chem.Soc.Dalton Trans.263-272 (1994)

[Publications] T.Ohno, K.Nozaki, A.Yoshimura, N.Ikeda, and T.Iguro: "Photoinduced Intramolecular Electron Transfer Reactions within donoracceptor Linkedcompounds in Solution and within Donor-Acceptor Ion-Pairs in Crystal" Res.Chem.Intermed.20. 807-814 (1994)

[Publications] M.Haga, M.M.Ali, S.Koseki, A.Yoshimura, K.Nozaki, and T.Ohno: "Synthesis, Electrochemistry and Photoexcited-State Properties of Dinuclear Rutheniumcomplexes Bridged by 2,6'-bis(2-pyridyl)-2,2':6,2"-thiazolo-[4,5-d]-benzothiazole." Inorg.Chim.Acta. 226. 17-24 (1994)

[Publications] T.Iguro, N.Ikeda, and T.Ohno: "Electron Transfer Quenching of the Excited MLCT State of Ru(II) in the Double Complex Salts[Ru(bpy)_3]_2[M(CN)_6]Cl・8H_2O(M=Co and Fe)." Inorg.chim.Acta. 226. 203-211 (1994)

[Publications] N.Fukazawa, H.Fukumura, H.Masuhara and J.Prochorow: "A Picosecond Diffuse Reflectance Laser Photolysis Study on Phenanthrene-Pyromellitic Dianhydride Charge-Transfer Crystal." Chem.Phys.Lett.220. 461-466 (1994)

[Publications] H.Fukumura and H.Masuhara: "The Mechanism of Dopant-Induced Laser Ablation. Possibility of Cyclic Multiphotonic Absorption in Excited States." Chem.Phys.Lett.221. 373-378 (1994)

[Publications] N.Fukazawa, H.Fukumura, and H.Masuhara: "Picosecond Diffuse Reflectance Laser Photolysis Study on 9,10-dichloroanthracene and 9,10-dibromoanthracene microcrystals" Chem.Phys.Lett.222. 123-128 (1994)

[Publications] H.Furutani, H.Fukumura, and H.Masuhara: "A.Nanosecond Time-Resolved Interferometric Study on Morphological Dytamics of Doped Poly(Methyl Methacrylare) Film upon Laser Ablation." Appl.Phys.Lett.65. 3413-3415 (1994)

[Publications] T.Ueda, R.Fujisawa, H.Fukumura, A.Itaya, and H.Masuhara: "Electronic Structure and Dynamics of Ionic Species in Thin Poly(N-Vinylcarbazole) Films Doped with Some Electron Acceptors as Revealed by Transient Absorption Spectroscopy." J.Phys.Chem.(in press). (1995)

[Publications] H.Fukumura, E.Takahashi, and H.Masuhara: "Time-Resolved Spectroscopic and Photographic Studies on Laser Ablation Mechanism of Doped Poly(Mathyl Metacrylate) Film" J.Phys.Chem.(in press). (1995)

[Publications] K.Watanabe, T.Asahi, and H.Masuhara: "Hole Diffusion-Controlled Geminate Charge Recombination Dynamics in Doped Poly(N-Vinylcarbazole) Films by Transient Absorption Spectroscopy." Chem.Phys.Lett.(in press). (1995)

[Publications] H.Fujiwara, T.Hayashi, H.Fukumura, and H.Masuhara: "Each Dopant can Absorb More than Ten Photons: Transient Absorbance Measurement at Excitation Laser Wavelength in Polymer Ablation." Appl.Phys.Lett.64. 2451-2453 (1994)

[Publications] Y.Tsuboi, H.Fukumura, and H.Masuhara: "Nanosecond Imaging Study on Laser Ablation of Liquid Benzene." Appl.Phys.Lett.64. 2745-2747 (1994)

[Publications] S.Hashimoto, N.Fukazawa, H.Fukumura, and H.Masuhara: "Diffuse Reflectance Laser Photolysis Study on Triplet Complex between Aromatics and T1+lncluded in TI-exchanged X-Type Zeolite." Chem.Phys.Lett.223. 493-500 (1994)

[Publications] H.Fukumura, Y.Kohji, K.Nagasawa, and H.Masuhara: "Laser Implantation of Pyrene Molecules into Poly(methyl Methacrylate) Films." J.Am.Chem.Soc.116. 10304-10305 (1994)

[Publications] Y.Tsuboi, K.Hatanaka, H.Fukumura, and H.Masuhara: "248nm Excimer Laser Ablation of Liquid Benzene Derivatives: A Relation between Ablation Threshold and Molecular Photochemical Reactivity." J.Phys.Chem.98. 11237-11241 (1994)

[Publications] M.Ichikawa, H.Fukumura, and H.Masuhara: "Picosecond Regular Reflection Spectroscopic Study on Ultrafast Photoinduced Heat Generation in Copper Phthanlocyanine Solid." J.Phys.Chem.98. 12211-12214 (1994)

[Publications] H.Nakagawa, Y.Koyama, and T.Okada: "Cytochrome c Electronic Structure Characterization toward the Analysis of Electron Transfer Mechanism." J.Biochem.115. 891-897 (1994)

[Publications] V.F.Kamalov, I.A.Struganova, Y.Koyama, and K.Yoshihara: "Two-Exciton Emission of BICJ-Aggregates" Chem.Phys.Lett.226. 132-136 (1994)

[Publications] L.Limantara, Y.Koyama, I.Katheder, and H.Scheer: "Transient Raman Spectroscopy of 15N-Substituted Bacteriochlorophyll a.An Empirical Assignment of T1 Raman Lines." Chem.Phys.Lett.227. 617-622 (1994)

[Publications] H.Nagae, M.Kuki, R.J.Cogdell, and Y.Koyama: "Shifts of the ^1Ag^-→^1Bu^+ Electronic Absorption of Carotenoids in Nonpolar and Polar Solvents." J.Chem.Phys.101. 6750-6765 (1994)

閑春夫群馬大学, 工学部, 教授 (40008454)