1992 年度実績報告書

常磁性種の活性とスピン間相互作用に関する物理化学的研究

研究課題

研究課題/領域番号	02303001
研究機関	横浜国立大学
研究代表者	樋口治郎横浜国立大学, 工学部, 教授 (20017875)
研究分担者	手老省三東北大学, 反応化学研究所, 助教授 (80111318) 工位武治大阪市立大学, 理学部, 教授 (10117955) 小尾欣一東京工業大学, 理学部, 教授 (10016090) 広田襄京都大学, 理学部, 教授 (90093301) 岩泉正基東北大学, 反応化学研究所, 教授 (70006295)
キーワード	常磁性種 / フリーラジカル / 励起三重項状態 / EPR(ESR) / 時間分解EPR / CIDEP / スピン間相互作用 / 金属錯体
研究概要	1.時間分解能と周波数分解能の向上を中心とした常磁性化学の研究法の開拓:時間分解EPR法については、装置の改良により多くの短寿命励起分子の動的挙動について詳細な研究が可能になってきた。また、CIDEP信号の定量的解析においては、過度回析格子分光法により、多くのラジカルの拡散過程が調べられた。他方、さらに短寿命の現象の解明可能なパルスEPR装置に加え、FTEPR装置も稼動した。 2.励起状態における常磁性種のスピン間相互作用の諸問題:個人の分子の最低励起三重項状態における電子スピン間相互作用の検討から、基庄状態と比べ構造変化の大きい分子の励起状態の構造,分子内水素結合を有し励起状態でケトエノール異性化を起す分子の構造と動的養動,フラーレン類の三重項状態の構造と動的養動等興味ある問題の解明が行われた。また、励起三重項多量体における分子問相互作用の研究から、他の方法では困難な同種分子間のエネルギー移動速度が求められた。 3.金属錯体における活性とスピン間相互作用:時間分解EPR等の実験を数種のクロム(III)錯体について行い、光励起後基底状態でスピン分極が起ることが見出された。地方モデルに錯体を用いて、銅酵素の配位構造の歪みと銅イオンの電子状態並びに酵素機能の相関について興味ある結果が得られた。また、二核錯体の金属原子間相互作用について、スピン交換と二重スピン分極機構の重要性が明らかにされた。 4.凝縮相捕足フリーラジカルにおける活性:これまで中性分子との構造変化を証明する情報の無かったアルカン類のα-カチオンラジカルについて、プロパン年数種のカチオンでは対称的構造から非対称構造に歪んでいることが見出された。他方、低温固相中の水素引き抜きで生じるアルキルラジカルをパルスEPR法で観測し、水素引き抜き速度がC-C交角振動の緩和速度に強く影響されることが明らかにされた。

研究成果

(25件)

すべてその他

すべて文献書誌 (25件)

[文献書誌] M.Mukai,S.Yamauchi,N.Hirota,and J.Higuchi: "Tiem-Resolved EPR and Phosphorescence Studies of the Lowest Excited Triplel State od Benzil" J. Phys. Chem.96. 9328-9331 (1992)
[文献書誌] M.Terazima,N.Hirota,H.Shinohara,and Y.Saito: "Time-Resolved EPR Inbestigation of Triplet State of C_<60> and C_<70>" Chem. Phys. Left. 195. 333-338 (1992)
[文献書誌] T.Ikoma, K.Akiyama, S.Tero-kubota, and Y.Ikegami: "Structural Effects on the Radiationless Transition from the T_1 States of Tropone Derivatives" J. Phys. Chem.97. 303-305 (1993)
[文献書誌] H.Yagi, T.Kaneshima, H.Torii, M.Matsuo, and J.Higuchi: "Effects of Counterion on the Triplet States of Zinc(II) Complexes with 1,10-Phenanthroline and 2,9-Dimethy1-1,10-Phenanthroline" Chem. Phys. Left. 197. 457-460 (1992)
[文献書誌] M.Kato, K.Sasano, M.Kimura,and S.Yamauchi: "Solid State Effect on the Phosphorescence Spectrum of Tris(3,3'-biisoquinoline)Ruthenium(II)" Chem. Left.1887-1890 (1992)
[文献書誌] A.Kawai, T.Okutsu, and K.Obi: "CIDEP in the Photsensitized Dissociation of Benzylchloride" Chem. Phys. Left.198. 637-640 (1992)
[文献書誌] K.Ohara, H.Murai, and K.Kuwata: "Time-Resolved ESR Studies on Photosensitized Reaction of Maleic Anhydride in Alcohols:Cidep Memory Transfer in Spin-Adduct Formation" Bull. Chem. Soc. Jpn.65. 1672-1678 (1992)
[文献書誌] A.Hanazeki, H.Murai, and K.Kuwata: "Photosensitized Triplet State of 1,3-Cyclodienes Detected by a Time-Resolved ESR Method" Chem. Phys. Left.197. 67-71 (1992)
[文献書誌] K.Fukui, K.Kojima, H.Ohya-Nishiguchi, and N.Hirota: "Metal-Thiolate Bondind Properties:Single-Crystal ESR,Susceptibililt,and Polarized Absorption Evidence for a Strong π Interaction in Tetrakis(thiophenolato)cohalt(II)" Inorg. Chiem.31. 1338-1344 (1992)
[文献書誌] M. Hanaya and M. Iwaizumi: "EPR Studies of Photochemical Reactions of Hexacarbonylbis-(η^5-2,4-cyclopentadien-1-yl)ditungsten,[CpW(CO)_3]_2, with Quinoncs" J. Org, Chem.435. 337-345 (1992)
[文献書誌] S. Kita, K. Uchida, R. Miyamoto, and M, Iwaizumi: "Spin-Spin Couplings in the Copper Acetate Hydrate Dimer Studied by Single Crystal ^<13>C-ENDOR for Zinc-Doped Copper Acetate Monohydrate" Chem. Left.1329-1332 (1992)
[文献書誌] M. Ebihara, K. Tokoro, K. Imaeda, K. Sakurai, H. Masuda, T. Kawamura: "Complexes of Silver(I) with Bis(dialkyldithiocabamato)-Platinum(II) as Ligand: Synthesis and Structure of [Pt_3(S_2CNPr_2)_6Ag_2](BF_4)_2 and [Pt_3(S_2CNBu_2)_6Ag_2](C10_4)_2" J. Chem. Soc., Chem. Commun.1591-1592 (1992)
[文献書誌] T. Otuka, A. Sekine, Y. Ohashi, and Y. Kaizu: "The Crystal Water Affecting ^2Eg→^4A_2g Relaxation in Tris(oxalato)chromate(III) Complexes" Bull. Chem. Soc. Jpn.65. 3378-3385 (1992)
[文献書誌] N.Ishikawa, O.Ohone, Y.Kauzu, and H.Kobayashi: "Localized Orbital Study on the Electronic Structure of Phthalocyanine Dimers" J. Phys. Chem.96. 8832-8839 (1992)
[文献書誌] M.Shiotani, K.Komaguti, J.Ohshita, M.Ishikawa, and I.Sjoqvist: "An Asymmetrically Distorted Structure of the 1-Methy1-silacycyclohexane Radical Cation:ESR Evidence" Chem. Phys. Left.188. 93-99 (1992)
[文献書誌] K.Komaguchi,M. Shiotani, M.Ishikawa, and K.Sasaki: "Structure and Ring-Puckering Motion of the σ-Localized Silacyclobutane Radical Cation:ESR Evidence" Chem. Phys. Left.200. 580-586 (1992)
[文献書誌] K.Toriyama and H.Okazaki: "Selectively Weakened C-C σ-Bond in Cation Radicals of Linear and Branched Pentanes as Studies by Electron Spin Resonance" J. Phys. Chem.96. 6986-6991 (1992)
[文献書誌] T.Ichikawa and II.Yoshida: "Selectivity of Alkyl Radical Formation from Branched Alkanes Studied by Electron Spin Resonace and Electron Spin Echo Spectroscopy" J. Phys. Chem.96. 7656-7661 (1992)
[文献書誌] T.IChikawa: "Application of ESE Spectroscopy to the Study of Radical Reactions in Solids" Pure Appl. Chem.64. 841-846 (1992)
[文献書誌] T.Ichikawa and II.Yoshida: "Effect of Solid Phase on the Selectivity of Hydrogen Abstraction from n-Alkanes. An Electron Spin Resonance and Electron Spin Echo Study" J. Phys. Chem.96. 7661-7664 (1992)
[文献書誌] Y.Fujisaka, J.Takahashi, T.Shida, T.Bally, and K.Roth: "Novel Photochemical Reaction of C_BII_<10> RAdical Cations" J. Phys. Chem.96. 2205-2210 (1992)
[文献書誌] II. Shinofara, II Sato, M. Ohkohci, Y. Ando, T. Kodama, T. Shida, T. Kato, and Y. saito: "Encapsualtion of a Scandium Trimer in C_<82>" Nature. 357. 52-54 (1992)
[文献書誌] M. Matsushita, T. Nakamura, T. Momose, T. Shida, Y. Teki, T. Takui T. Kinoshita, K. Itoh: "Novel Oranic Ions of Hith-Spiy States II.: Determination of the Spin Multiplicity of the Ground State and _1H-ENDOR Study of the Monoanion of m-Phenylenebis(Phenylmethylene)" J. Am. Chem. Soc.114. 7470-7475 (1992)
[文献書誌] J. Yamauchi, T. Sugimoto, Y. Arai, M. Sakaguchi, Z. Yoshida: "Redox Behavior and Stable Anion Radicals of Cyclic Polycalicenes" J. Chem. Soc., Perkin Trans. 2. 1959-1962 (1991)
[文献書誌] K. Yoshizawa, T. Tanaka, T. Yamabe, and J. Yamauchi: "Ferromagnetic Interaction in Poly(m-aniline): Electron Spin Resonace and Magnetic Susceptibility" J. Chem. Soc. Jpn.65. 2016-2020 (1992)

1992 年度 実績報告書

常磁性種の活性とスピン間相互作用に関する物理化学的研究

研究代表者

樋口 治郎 横浜国立大学, 工学部, 教授 (20017875)

研究成果

[文献書誌] M.Mukai,S.Yamauchi,N.Hirota,and J.Higuchi: "Tiem-Resolved EPR and Phosphorescence Studies of the Lowest Excited Triplel State od Benzil" J. Phys. Chem.96. 9328-9331 (1992)

[文献書誌] M.Terazima,N.Hirota,H.Shinohara,and Y.Saito: "Time-Resolved EPR Inbestigation of Triplet State of C_<60> and C_<70>" Chem. Phys. Left. 195. 333-338 (1992)

[文献書誌] T.Ikoma, K.Akiyama, S.Tero-kubota, and Y.Ikegami: "Structural Effects on the Radiationless Transition from the T_1 States of Tropone Derivatives" J. Phys. Chem.97. 303-305 (1993)

[文献書誌] H.Yagi, T.Kaneshima, H.Torii, M.Matsuo, and J.Higuchi: "Effects of Counterion on the Triplet States of Zinc(II) Complexes with 1,10-Phenanthroline and 2,9-Dimethy1-1,10-Phenanthroline" Chem. Phys. Left. 197. 457-460 (1992)

[文献書誌] M.Kato, K.Sasano, M.Kimura,and S.Yamauchi: "Solid State Effect on the Phosphorescence Spectrum of Tris(3,3'-biisoquinoline)Ruthenium(II)" Chem. Left.1887-1890 (1992)

[文献書誌] A.Kawai, T.Okutsu, and K.Obi: "CIDEP in the Photsensitized Dissociation of Benzylchloride" Chem. Phys. Left.198. 637-640 (1992)

[文献書誌] K.Ohara, H.Murai, and K.Kuwata: "Time-Resolved ESR Studies on Photosensitized Reaction of Maleic Anhydride in Alcohols:Cidep Memory Transfer in Spin-Adduct Formation" Bull. Chem. Soc. Jpn.65. 1672-1678 (1992)

[文献書誌] A.Hanazeki, H.Murai, and K.Kuwata: "Photosensitized Triplet State of 1,3-Cyclodienes Detected by a Time-Resolved ESR Method" Chem. Phys. Left.197. 67-71 (1992)

[文献書誌] K.Fukui, K.Kojima, H.Ohya-Nishiguchi, and N.Hirota: "Metal-Thiolate Bondind Properties:Single-Crystal ESR,Susceptibililt,and Polarized Absorption Evidence for a Strong π Interaction in Tetrakis(thiophenolato)cohalt(II)" Inorg. Chiem.31. 1338-1344 (1992)

[文献書誌] M. Hanaya and M. Iwaizumi: "EPR Studies of Photochemical Reactions of Hexacarbonylbis-(η^5-2,4-cyclopentadien-1-yl)ditungsten,[CpW(CO)_3]_2, with Quinoncs" J. Org, Chem.435. 337-345 (1992)

[文献書誌] S. Kita, K. Uchida, R. Miyamoto, and M, Iwaizumi: "Spin-Spin Couplings in the Copper Acetate Hydrate Dimer Studied by Single Crystal ^<13>C-ENDOR for Zinc-Doped Copper Acetate Monohydrate" Chem. Left.1329-1332 (1992)

[文献書誌] T. Otuka, A. Sekine, Y. Ohashi, and Y. Kaizu: "The Crystal Water Affecting ^2Eg→^4A_2g Relaxation in Tris(oxalato)chromate(III) Complexes" Bull. Chem. Soc. Jpn.65. 3378-3385 (1992)

[文献書誌] N.Ishikawa, O.Ohone, Y.Kauzu, and H.Kobayashi: "Localized Orbital Study on the Electronic Structure of Phthalocyanine Dimers" J. Phys. Chem.96. 8832-8839 (1992)

[文献書誌] M.Shiotani, K.Komaguti, J.Ohshita, M.Ishikawa, and I.Sjoqvist: "An Asymmetrically Distorted Structure of the 1-Methy1-silacycyclohexane Radical Cation:ESR Evidence" Chem. Phys. Left.188. 93-99 (1992)

[文献書誌] K.Komaguchi,M. Shiotani, M.Ishikawa, and K.Sasaki: "Structure and Ring-Puckering Motion of the σ-Localized Silacyclobutane Radical Cation:ESR Evidence" Chem. Phys. Left.200. 580-586 (1992)

[文献書誌] K.Toriyama and H.Okazaki: "Selectively Weakened C-C σ-Bond in Cation Radicals of Linear and Branched Pentanes as Studies by Electron Spin Resonance" J. Phys. Chem.96. 6986-6991 (1992)

[文献書誌] T.Ichikawa and II.Yoshida: "Selectivity of Alkyl Radical Formation from Branched Alkanes Studied by Electron Spin Resonace and Electron Spin Echo Spectroscopy" J. Phys. Chem.96. 7656-7661 (1992)

[文献書誌] T.IChikawa: "Application of ESE Spectroscopy to the Study of Radical Reactions in Solids" Pure Appl. Chem.64. 841-846 (1992)

[文献書誌] T.Ichikawa and II.Yoshida: "Effect of Solid Phase on the Selectivity of Hydrogen Abstraction from n-Alkanes. An Electron Spin Resonance and Electron Spin Echo Study" J. Phys. Chem.96. 7661-7664 (1992)

[文献書誌] Y.Fujisaka, J.Takahashi, T.Shida, T.Bally, and K.Roth: "Novel Photochemical Reaction of C_BII_<10> RAdical Cations" J. Phys. Chem.96. 2205-2210 (1992)

[文献書誌] II. Shinofara, II Sato, M. Ohkohci, Y. Ando, T. Kodama, T. Shida, T. Kato, and Y. saito: "Encapsualtion of a Scandium Trimer in C_<82>" Nature. 357. 52-54 (1992)

[文献書誌] J. Yamauchi, T. Sugimoto, Y. Arai, M. Sakaguchi, Z. Yoshida: "Redox Behavior and Stable Anion Radicals of Cyclic Polycalicenes" J. Chem. Soc., Perkin Trans. 2. 1959-1962 (1991)

[文献書誌] K. Yoshizawa, T. Tanaka, T. Yamabe, and J. Yamauchi: "Ferromagnetic Interaction in Poly(m-aniline): Electron Spin Resonace and Magnetic Susceptibility" J. Chem. Soc. Jpn.65. 2016-2020 (1992)

1992 年度実績報告書

樋口治郎横浜国立大学, 工学部, 教授 (20017875)