1989 Fiscal Year Annual Research Report

常磁性不安定化学種の構造ならびに生成と反応の動力学に関する研究

Research Project

Project/Area Number	62303001
Research Institution	Tohoku University
Principal Investigator	池上雄作東北大学, 非水溶液化学研究所, 教授 (60006294)
Co-Investigator(Kenkyū-buntansha)	岩泉正基東北大学, 非水溶液化学研究所, 教授 (70006295) 樋口治郎横浜国立大学, 工学部, 教授 (20017875)
Keywords	電磁性分子 / 不安定化学種 / フリ-ラジカル / 勃起三重項状態 / 電子スピン共鳴 / 時間分解ESR / 遷移金属錯体
Research Abstract	1.高時間分解ESR法による常磁性化学種の生成・反応動力学:時間分解ESR法が光反応過程と勃起三重種項状態の研究に常套手段として用いられるようになり、研究対象が広がってトリメチレンメタン生成系、ポルフイリンとキノンとの電子移動反応、アルキルコバロキシムの光化学初期過程、塩化ベンジル類の光分解機構、ピリジン誘導体の光化学反応などの新しい成果が得られた。パルスESR法利用への期待は残されたが、時間分解ESR法による成果は確実は地盤をつくった。 2.常磁性勃起分子の電子状態と緩和:芳香族カルボニル化合物やアザベンゼン類の勃起三重項状態が種々の実験結果をもとに、nπ^とππ^の混合の問題を中心に議論され、その解釈はほぼ完結した。三重項副準位のスピン分極、スピン分極保持T-Tエネルギ-移動は、勃起状態反応動力学として多くの例が示された。一方分子集合体の電子スピン状態との関連で、有機ラジカル結晶の磁性に関する研究が進展をみせた。 3.凝縮相捕促不安定常磁性種の構造と反応:飽和炭化水素カチオンラジカルの電子状態や分子運動に関する研究、イオン対のダイナミックス有機強磁性体モデル分子の電子構造、ENDOR法ハバ-ドハミルトンアンに理論計算を用いたスピン整列機構の新しい解釈が成功している。 4.錯体、有機金属常磁性種の構造と反応:銅(II)錯体など常磁性金属錯体を対象にしたENDOR法やラピッドスキャンENDOR法による錯体構造の研究やESEEM法など新しい方法を取り入れた研究成果が出ている。生体内遷移金属の挙動を意識した基礎研究は地道につついている。 5.生体関連常磁性の生成、構造および反応:生体系活性酸素ラジカルのスピントラッフ法、紫外線白内障の成因となるフリ-ラジカル、スピン標識イオンキャリヤ-をプロ-ブとする脂質二重膜輸送系の研究などつぎつぎと新しい研究へ進み、これからの展開が期待される。

Research Products

(38 results)

All Other

All Publications (38 results)

[Publications] Y.Ikegami,T.Muramatsu,K.Hanaya.: "Photosensitive Cyclomer Formation of 1,1'-(1,2-Ethanediyl)bis(phridinyl)Diradical and Its Derivatives" J.Am.Chem.Soc.111. 5782-5787 (1989)
[Publications] K.Akiyama,A.Kaneko,S.Terokubota,Y.Ikegami: "Spin Polarization Conservation During Triplet-Triplet Energy Transfer in Fluid Solution as Studied by Time-Resolved ESR Spectroscopy" J.Am.Chem.Soc.in press.
[Publications] M.Yagi,K.Mikuni,K.Takano,Y.Shioya,J.Higuchi: "Time-Resolved Electtron Spin Resonance Study of the Nonphosphorescent Triplet State of trans-Diazastilbene" J.Phys.Chem.93. 4714-4715 (1989)
[Publications] M.Yagi,H.Shirai,J.Ohta,J.Higuchi: "The Effects of Conformation and Coordination to Zinc(II)Ions on the Lowest Triplett State of 6,6'-Dimethy1-2,2'-Bipyridine:A Time-Resolved ESR Study" Chem.Phys.Lett.160. 13-16 (1989)
[Publications] Y.Sueishi,k.Kuwata: "Pressure Effects on the Electron Spin Relaxation of Several Radicals in Solution" Chem.Phys.Lett.160. 640-643 (1989)
[Publications] H.Murai,K.Kuwata: "CIDEP of Transient Radical-Ion Pair:Photolysis of N,N,N',N'-Tetramethyl-p-phenylenediamine in 2-Propanol" Chem.Phys.Lett.164. 567-570 (1989)
[Publications] S.Yamauchi,N.Hirota,S.Takahara,H.Misawa,K.Sawabe,H.Sakuragi,K.Tokumaru: "A Time-Resolved EPR Study of Photodecomposition of Dibenzoyl Peroxides in Carbon Tetrachloride" J.Am.Chem.Soc.111. 4402-4407 (1989)
[Publications] K.Tominaga,S.Yamauchi,N.Hirota: "A CIDEP Study on the Hydrogen Abstraction Reaction of Carbonyls with Alkane,Position Dependence of the Reaction Rate" J.Phys.Chem.
[Publications] H.Hiratsuka,K.Mori,H.Shizuka,M.Fukushima,K.Obi: "Emitting States of Benzyl,p-Fluorobenzyl and p-Cyanobenzyl Radicals" Chem.Phys.Lett.157. 35-40 (1989)
[Publications] T.Okutsu,A.Kawai,K.obi: "Derect Observation of the Triplet-Triplet Energy Transfer to the Second Excited Triplet State" J.Phys.Chem.93. 7757-7759 (1989)
[Publications] M.Terazima,K.Maeda,T.Azumi,Y.Tanimoto,N.Okada,M.Ito: "CIDEP Studies on th Intramolecular Hydrogen Abstraction Reaction of Polymethylene Linked System.Population Relaxation Between the S-T_0States" Chem.Phys.Lett.164. 562-566 (1989)
[Publications] N.Okabe,T.Ikeyama t.Azumi: "Spin-Sublevel Properties of the π,π^*Triplet State of 2,2'-Bipyridine.Is Our-of plane Component Most Emmisive?" Chem.Phys.Lett.165. 24-27 (1990)
[Publications] K.Awaga,H.Okamoto,T.Mitani,Y.Maruyama,T.Sugano,M.Kinoshita: "Spin-Soliton Excitation in One-Dimensional Alternating Antiferromagnetic System of Galvinoxyl Single Crystal" Solid State Commun.71. 1173-1177 (1989)
[Publications] Y.Kubozono,M.Ata,M.Aoyagi,t.Fujita,N.fukami,Y.Gondo: "Polarized Absorption Spectra of Some Aromatic Radical Anions in Stretched Polyethylene Films" J.Chem.Soc.,Faraday Trans.2. 85. 1477-1486 (1989)
[Publications] M.Ata,Y.Kubozono,Y.Suzuki,M.Aoyagi,Y.Gondo: "Induced Circular Dichroism and Molecular Orientations of β-Cyclodextrin Inclusion Complexes with 9,10-Anthraquinone and 9,10-Phenanthrenequinone" Bull.Chem.Soc.Jpn.62. 3706-3708 (1989)
[Publications] T.Ichikawa,M.Shiotani,N.Ohta,H.Katsumata: "ESR and Optical Studies of Solute n-Alkane Cations Formed in γ-Irradiated n-Pentane and n-Hexane Matrices" J.Phys.Chem.93. 3826-3831 (1989)
[Publications] M.Lindgren,M.Shiotani,N.Ohta,T.Ichikawa,L.Sjogvist: "ESR Evidence of a Distorted ^2Ag Electronic Structure of the Methylcyclohexane Radical Cation" Chem.Phys.Lett.161. 127-130 (1989)
[Publications] K.Tanaka,S.Yamashita,T.Yamabe,J.Yamauchi,Y.Deguchi: "ESR Studies of Polycondensate of Fused Polynuclear Aromatics(COPNA)Resin with Ferromagnetic Behaviour" Solid State Commun.71. 627-628 (1989)
[Publications] K.Tanaka,Y.Deguchi,T.Hoshiko,K.Konish,K.Takahashi,J.Yamauchi: "Magnetic Behavior of Organic Free Radicals with Localized and Delocalized Electrons" J.Phys.soc.Jpn.58. 3361-3370 (1989)
[Publications] Y.Yokoyama,T.Iwai,N.Kera,I.Hitomi,Y.Kurita: "Steric Effect of Alkylidene Groups of Furylfulgides on th Photochromic Behavior" Chem.Lett.in press.
[Publications] T.Ichikawa,H.Yoshida: "Solvation Structure of Excess Electrons in Ethanol and Ethanol/2-Methyltetrahydrofuran Mixture" J.Phys.Chem. 93. 5943-5947 (1989)
[Publications] T.Ichikawa,H.Yoshida,J.Westerling: "Coupling Structure for Loop-Gap Resonator" J.Magn.Reson.85. 132 (1989)
[Publications] I.Fujita,Y.Teki,T.Takui,T.Kinoshita,K.Itoh,F.Miko,Y.Sawaki,H.Iwamura: "Design,Preparation and ESR Detection of a Ground-State Undecet(S=5)Hydrocarbon" J.Am.Chem.Soc.in press.
[Publications] Y.Teki T.Takui,M.Kitano,K.Itoh: "Intramolecular Spin Alignment in Organic High-Spin Molecules via an Oxygen-Atom Bridge.A Heisenberg Hamiltonian Approach" Chem.Phys.Lett.Submitted.
[Publications] K.Ushida,T.Shida,K.Shimokoshi: "Photoinduced Isomerization Observed for Ring-Opened Radical Cations of Methyl-Substituted Ethylene Oxides" J.Phys.Chem.93. 5388-5393 (1989)
[Publications] M.Matsushita,T.Momose,T.Kato,T.Shida: "Molecular Motion of the Radical Cations in the Condensed Phase as Studied by ESR:Diazabenzenes" Chem.Phys.Lett.161. 461-465 (1989)
[Publications] K.Matsuura,K.Nunome,M.Okazaki,K.Toriyama,M.Iwasaki: "Isotope Effect on the Static Distortion and the Dynamics of Partially Deuteriated Jahn-Teller Active Radicals:Cyclopropane-1,1-d_2" J.Phys.Chem.93. 6642-6645 (1989)
[Publications] M.Okazaki,Y.Tai,R.Nakagaki,K.Nunome,K.Toriyama: "The Excimer Formation of Pyrene as a Probe to Investigate the Recombination Process of Geminate Pair:ODESR and Fluorescence Study on the Dilute Phyrene Solution in Squalane" Chem.Phys.Lett.in press.
[Publications] M.Kira,M.Akiyama,M.Ichinose,H.Sakurai: "ESR Study of 2-Substituted 2-Adamantyl Radicals.Configuration and Long-Range Hyperfine Interaction" J.Am.Chem.Soc.111. 8256-8262 (1989)
[Publications] M.Hanaya,M.Iwaizumi: "EPR Studies of the Paramagnetic Complexes Produced in the Photochemical Reactions of Hexacarbonylbis(n^5-2,4-cycloo-pentadien-1-yl)dimolybdenum,[CpMo(CO)_3]_2,with p-Benzoquinones" Organometallics. 8. 672-676 (1989)
[Publications] M.Hanaya,M.Iwaizumi: "EPR Study of th Precursorss of Chelate Paramagnetic Complexes formed in Photochemical Reactions of [Mo(cp)-(CO)_3]_2(cp=n^5-C_5H_5 with o-Quinones" Bull.Chem.Soc.Jpn.63. 275-277 (1990)
[Publications] A.Hasegawa,M.C.R.Symons,M.Shiotani: "Electron Spin Resonance Spectra and Structure of the Radical Cations of Dibromalkanes and Monobromoalkanes" J.Chem.Soc.,Perkin Trans.2. 657-665 (1989)
[Publications] A.Hasegawa,J.L.Wyatt,M.C.R.Symons: "The Radical Cation of Tetraphosphorus:ESR Spectra and Structure" J.Chem.Soc.,Chem.Commun.in press.
[Publications] T.Kawamura,H.Katayama,H.Nishikawa,T.Yamabe: "Ligand Dependence of Electronic Configuration of the Rh-Rh Bond in Rh^5 Complexes as Studied by Electron Spin Resonance and Electrochemistry" J.Am.Chem.Soc.111. 8156-8160 (1989)
[Publications] K.Tajima,J.Jinno,K.Ishizu,H.Sakurai,H.Ohya-Nishiguchi: "Direct Evidence of Heme-tert-Butylperoxide Adduct Formation Demonstrated by Simultaneous ESR and Optical Measurements" Inorg.Chem.28. 709-715 (1989)
[Publications] K.Tajima,M.Miyoshi,M.Furutani,Y.Fujimura,K.Mukai,K.Ishizu: "ENDOR Studies on Complexation Reaction between Spin Labeled Crown Ether and Alkaline Metal Salts" Bull.Chem.Soc.Jpn.62. 2061-2063 (1989)
[Publications] J.Murakami,M.Okazaki,T.Shiga: "Near UV-Induced Free Radicals in Ocular Lens,Studied by ESR and Spin Trapping" Photochem.Photobiol.49. 465-473 (1989)
[Publications] N.Murase,T.Watanabe: "Nucelear Magnetic Relaxation Studies of the Compartmentalized Water in Cross-linked polymer Gels" Magn.Reson.Med.9. 1-7 (1989)

1989 Fiscal Year Annual Research Report

常磁性不安定化学種の構造ならびに生成と反応の動力学に関する研究

Principal Investigator

池上 雄作 東北大学, 非水溶液化学研究所, 教授 (60006294)

Research Products

[Publications] Y.Ikegami,T.Muramatsu,K.Hanaya.: "Photosensitive Cyclomer Formation of 1,1'-(1,2-Ethanediyl)bis(phridinyl)Diradical and Its Derivatives" J.Am.Chem.Soc.111. 5782-5787 (1989)

[Publications] K.Akiyama,A.Kaneko,S.Terokubota,Y.Ikegami: "Spin Polarization Conservation During Triplet-Triplet Energy Transfer in Fluid Solution as Studied by Time-Resolved ESR Spectroscopy" J.Am.Chem.Soc.in press.

[Publications] M.Yagi,K.Mikuni,K.Takano,Y.Shioya,J.Higuchi: "Time-Resolved Electtron Spin Resonance Study of the Nonphosphorescent Triplet State of trans-Diazastilbene" J.Phys.Chem.93. 4714-4715 (1989)

[Publications] M.Yagi,H.Shirai,J.Ohta,J.Higuchi: "The Effects of Conformation and Coordination to Zinc(II)Ions on the Lowest Triplett State of 6,6'-Dimethy1-2,2'-Bipyridine:A Time-Resolved ESR Study" Chem.Phys.Lett.160. 13-16 (1989)

[Publications] Y.Sueishi,k.Kuwata: "Pressure Effects on the Electron Spin Relaxation of Several Radicals in Solution" Chem.Phys.Lett.160. 640-643 (1989)

[Publications] H.Murai,K.Kuwata: "CIDEP of Transient Radical-Ion Pair:Photolysis of N,N,N',N'-Tetramethyl-p-phenylenediamine in 2-Propanol" Chem.Phys.Lett.164. 567-570 (1989)

[Publications] S.Yamauchi,N.Hirota,S.Takahara,H.Misawa,K.Sawabe,H.Sakuragi,K.Tokumaru: "A Time-Resolved EPR Study of Photodecomposition of Dibenzoyl Peroxides in Carbon Tetrachloride" J.Am.Chem.Soc.111. 4402-4407 (1989)

[Publications] K.Tominaga,S.Yamauchi,N.Hirota: "A CIDEP Study on the Hydrogen Abstraction Reaction of Carbonyls with Alkane,Position Dependence of the Reaction Rate" J.Phys.Chem.

[Publications] H.Hiratsuka,K.Mori,H.Shizuka,M.Fukushima,K.Obi: "Emitting States of Benzyl,p-Fluorobenzyl and p-Cyanobenzyl Radicals" Chem.Phys.Lett.157. 35-40 (1989)

[Publications] T.Okutsu,A.Kawai,K.obi: "Derect Observation of the Triplet-Triplet Energy Transfer to the Second Excited Triplet State" J.Phys.Chem.93. 7757-7759 (1989)

[Publications] M.Terazima,K.Maeda,T.Azumi,Y.Tanimoto,N.Okada,M.Ito: "CIDEP Studies on th Intramolecular Hydrogen Abstraction Reaction of Polymethylene Linked System.Population Relaxation Between the S-T_0States" Chem.Phys.Lett.164. 562-566 (1989)

[Publications] N.Okabe,T.Ikeyama t.Azumi: "Spin-Sublevel Properties of the π,π^*Triplet State of 2,2'-Bipyridine.Is Our-of plane Component Most Emmisive?" Chem.Phys.Lett.165. 24-27 (1990)

[Publications] K.Awaga,H.Okamoto,T.Mitani,Y.Maruyama,T.Sugano,M.Kinoshita: "Spin-Soliton Excitation in One-Dimensional Alternating Antiferromagnetic System of Galvinoxyl Single Crystal" Solid State Commun.71. 1173-1177 (1989)

[Publications] Y.Kubozono,M.Ata,M.Aoyagi,t.Fujita,N.fukami,Y.Gondo: "Polarized Absorption Spectra of Some Aromatic Radical Anions in Stretched Polyethylene Films" J.Chem.Soc.,Faraday Trans.2. 85. 1477-1486 (1989)

[Publications] M.Ata,Y.Kubozono,Y.Suzuki,M.Aoyagi,Y.Gondo: "Induced Circular Dichroism and Molecular Orientations of β-Cyclodextrin Inclusion Complexes with 9,10-Anthraquinone and 9,10-Phenanthrenequinone" Bull.Chem.Soc.Jpn.62. 3706-3708 (1989)

[Publications] T.Ichikawa,M.Shiotani,N.Ohta,H.Katsumata: "ESR and Optical Studies of Solute n-Alkane Cations Formed in γ-Irradiated n-Pentane and n-Hexane Matrices" J.Phys.Chem.93. 3826-3831 (1989)

[Publications] M.Lindgren,M.Shiotani,N.Ohta,T.Ichikawa,L.Sjogvist: "ESR Evidence of a Distorted ^2Ag Electronic Structure of the Methylcyclohexane Radical Cation" Chem.Phys.Lett.161. 127-130 (1989)

[Publications] K.Tanaka,S.Yamashita,T.Yamabe,J.Yamauchi,Y.Deguchi: "ESR Studies of Polycondensate of Fused Polynuclear Aromatics(COPNA)Resin with Ferromagnetic Behaviour" Solid State Commun.71. 627-628 (1989)

[Publications] K.Tanaka,Y.Deguchi,T.Hoshiko,K.Konish,K.Takahashi,J.Yamauchi: "Magnetic Behavior of Organic Free Radicals with Localized and Delocalized Electrons" J.Phys.soc.Jpn.58. 3361-3370 (1989)

[Publications] Y.Yokoyama,T.Iwai,N.Kera,I.Hitomi,Y.Kurita: "Steric Effect of Alkylidene Groups of Furylfulgides on th Photochromic Behavior" Chem.Lett.in press.

[Publications] T.Ichikawa,H.Yoshida: "Solvation Structure of Excess Electrons in Ethanol and Ethanol/2-Methyltetrahydrofuran Mixture" J.Phys.Chem. 93. 5943-5947 (1989)

[Publications] T.Ichikawa,H.Yoshida,J.Westerling: "Coupling Structure for Loop-Gap Resonator" J.Magn.Reson.85. 132 (1989)

[Publications] I.Fujita,Y.Teki,T.Takui,T.Kinoshita,K.Itoh,F.Miko,Y.Sawaki,H.Iwamura: "Design,Preparation and ESR Detection of a Ground-State Undecet(S=5)Hydrocarbon" J.Am.Chem.Soc.in press.

[Publications] Y.Teki T.Takui,M.Kitano,K.Itoh: "Intramolecular Spin Alignment in Organic High-Spin Molecules via an Oxygen-Atom Bridge.A Heisenberg Hamiltonian Approach" Chem.Phys.Lett.Submitted.

[Publications] K.Ushida,T.Shida,K.Shimokoshi: "Photoinduced Isomerization Observed for Ring-Opened Radical Cations of Methyl-Substituted Ethylene Oxides" J.Phys.Chem.93. 5388-5393 (1989)

[Publications] M.Matsushita,T.Momose,T.Kato,T.Shida: "Molecular Motion of the Radical Cations in the Condensed Phase as Studied by ESR:Diazabenzenes" Chem.Phys.Lett.161. 461-465 (1989)

[Publications] K.Matsuura,K.Nunome,M.Okazaki,K.Toriyama,M.Iwasaki: "Isotope Effect on the Static Distortion and the Dynamics of Partially Deuteriated Jahn-Teller Active Radicals:Cyclopropane-1,1-d_2" J.Phys.Chem.93. 6642-6645 (1989)

[Publications] M.Okazaki,Y.Tai,R.Nakagaki,K.Nunome,K.Toriyama: "The Excimer Formation of Pyrene as a Probe to Investigate the Recombination Process of Geminate Pair:ODESR and Fluorescence Study on the Dilute Phyrene Solution in Squalane" Chem.Phys.Lett.in press.

[Publications] M.Kira,M.Akiyama,M.Ichinose,H.Sakurai: "ESR Study of 2-Substituted 2-Adamantyl Radicals.Configuration and Long-Range Hyperfine Interaction" J.Am.Chem.Soc.111. 8256-8262 (1989)

[Publications] M.Hanaya,M.Iwaizumi: "EPR Studies of the Paramagnetic Complexes Produced in the Photochemical Reactions of Hexacarbonylbis(n^5-2,4-cycloo-pentadien-1-yl)dimolybdenum,[CpMo(CO)_3]_2,with p-Benzoquinones" Organometallics. 8. 672-676 (1989)

[Publications] M.Hanaya,M.Iwaizumi: "EPR Study of th Precursorss of Chelate Paramagnetic Complexes formed in Photochemical Reactions of [Mo(cp)-(CO)_3]_2(cp=n^5-C_5H_5 with o-Quinones" Bull.Chem.Soc.Jpn.63. 275-277 (1990)

[Publications] A.Hasegawa,M.C.R.Symons,M.Shiotani: "Electron Spin Resonance Spectra and Structure of the Radical Cations of Dibromalkanes and Monobromoalkanes" J.Chem.Soc.,Perkin Trans.2. 657-665 (1989)

[Publications] A.Hasegawa,J.L.Wyatt,M.C.R.Symons: "The Radical Cation of Tetraphosphorus:ESR Spectra and Structure" J.Chem.Soc.,Chem.Commun.in press.

[Publications] T.Kawamura,H.Katayama,H.Nishikawa,T.Yamabe: "Ligand Dependence of Electronic Configuration of the Rh-Rh Bond in Rh^5 Complexes as Studied by Electron Spin Resonance and Electrochemistry" J.Am.Chem.Soc.111. 8156-8160 (1989)

[Publications] K.Tajima,J.Jinno,K.Ishizu,H.Sakurai,H.Ohya-Nishiguchi: "Direct Evidence of Heme-tert-Butylperoxide Adduct Formation Demonstrated by Simultaneous ESR and Optical Measurements" Inorg.Chem.28. 709-715 (1989)

[Publications] K.Tajima,M.Miyoshi,M.Furutani,Y.Fujimura,K.Mukai,K.Ishizu: "ENDOR Studies on Complexation Reaction between Spin Labeled Crown Ether and Alkaline Metal Salts" Bull.Chem.Soc.Jpn.62. 2061-2063 (1989)

[Publications] J.Murakami,M.Okazaki,T.Shiga: "Near UV-Induced Free Radicals in Ocular Lens,Studied by ESR and Spin Trapping" Photochem.Photobiol.49. 465-473 (1989)

[Publications] N.Murase,T.Watanabe: "Nucelear Magnetic Relaxation Studies of the Compartmentalized Water in Cross-linked polymer Gels" Magn.Reson.Med.9. 1-7 (1989)

池上雄作東北大学, 非水溶液化学研究所, 教授 (60006294)