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

1991 Fiscal Year Annual Research Report

• Project/Area Number: 02303001
• Research Institution: Yokohama National University
• Principal Investigator: 樋口 治郎 横浜国立大学, 工学部, 教授 (20017875)
• Co-Investigator(Kenkyū-buntansha): 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, 助教授 (10117955) ; 小尾 欣一 東京工業大学, 理学部, 教授 (10016090) ; 廣田 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)
• Keywords: 常磁性種 / フリ-ラジカル / 励起三重項状態 / ESR / 時間分解ESR / ENDOR / スピン間相互作用 / 金属錯体

Research Abstract

1.時間分解能と周波数分解能向上を中心とする常磁性化学研究法の開拓: 時間分解ESR技法については,前年度にも増し,パルスESR法を用いた興味ある実験結果が得られているが,装置並びに測定上の問題点を含め,全般的な研究方法に関する検討が行われた。さらに,高周波ESR装置の製作上の問題と,ENDOR測定における高速化の問題についても,前年度に引き続き,最先端の研究を目指した検討が行れ,高速測定のための装置の改良が進められている。
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: CIDEP法をはじめ、時間分解ESR法の実験が引き続き順調に行れ、芳香族分子の励起三重項状態に関する最先端の研究成果が多数報告されている。特に、分子内水素移動の問題については、光励起三重項状態に限らず、光化学反応により生成する熱励起三重項状態についても興味ある例が明らかになり、スピン間相互作用に関し注目すべき結果が得られた。
3.金属錯体における活性とスピン間相互作用: 銅(II)をはじめ数種の常磁性イオン錯体の基底状態と、亜鉛(II)等数種の反磁性イオン錯体の励起三重項状態について、ESR法を中心とした測定が順調に行れた。特に、前者においてはENDOR法を併用することにより分子の構造に関し著しい成果を挙げており、後者においては時間分解法を併用することにより生成の動的過程に興味ある結果が得られている。
4.凝縮相補足フリ-ラジカルにおける活性: 高スピン分子種については,昨年度初めて報告された高スピンイオンラジカルの研究に加え,スピン多種度が現在最高の分子種が見出され、ESR法並びにENDOR法による注目すべき実験が行われた。また、二重項状態のラジカルについては、昨年度に引き続き、特にカチオンラジカルについて著しい発展があり、ラジカルの構造解析を含め興味ある研究が行れた。

Research Products

• [Publications] K.Tominaga,S.Yamauchi and N.Hirota: "Chemically Induced Dynamic Electron Polarization Study of the Rates of Hydrogen Abstraction Reactions of Carbonyls.Position Dependence and Deuterium Effect" J.Phys.Chem.95. 3671-3676 (1991)
• [Publications] M.Baba,T.Kamei,M.Kiritani,S.Yamauchi and N.Hirota: "A Phosphorescence Study of JetーCooled Xanthone" Chem.Phys.Lett.185. 354-358 (1991)
• [Publications] M.Terazima and N.Hirota: "Measurement of the Quantum Yield of Triplet Formation and Short Triplet Lifetimes by the Transient Grating Technique" J.Chem.Phys.95. 6490-6495 (1991)
• [Publications] K.Fukui,H.OhyaーNishiguchi,and N.Hirota: "ESR and Magnetic Susceptibility Studies on HighーSpin Tetrahedral cobalt(II)ーThiolate Complexes:An Approach to RubredoxinーType Active Sites" Bull.Chem.Soc.Jpn.64. 1205-1212 (1991)
• [Publications] J.Jinno,M.Shigematsu,K.Tajima,H.Sakurai,H.OhyaーNishiguchi,and K.Ishizu: "Coordination Structure and Chemical Reactivity of HemoproteinーButyl Peroxide Complex" Biochem.Biophys.Res.Commun.176. 675-681 (1991)
• [Publications] Y.Ueda,N.Yumoto,M.Tokushige,K.Fukui,and H.OhyaーNishiguchi: "Purification and Characterization of Two Types of Fumarase from Esherichia Coli" J.Biochem.109. 728-733 (1991)
• [Publications] Y.Miura,K.Inui,F.Yamaguchi,M.Ionue,Y.Teki,T.Takui,and K.Itoh: "Molecular Design,Shythesis and Magnetic Characterization of Poly(phenylacetylene) with piーToporegulated Pendant Nitronyl Radicals as Models for Organic Superparaー and Ferromagnets" J.Pol.Sci.(1992)
• [Publications] M.Matsushita,T.Nakamura,T.Momose,T.Shida,Y.Teki,T.Takui,T.Kinoshita,and K.Itoh: "Novel Organic Ions of HighーSpin States II.:Determination of the Spin Multiplicity of the Ground State and ^1HーENDOR Study of the Monoanion of mーPhenylenebis(phenylmethylene)" J.Am.Chem.Soc.
• [Publications] Y.Teki,T.Takui,and K.Itoh: "Intramolecular Spin Alignment in Organic HighーSpin Molecules via an OxygenーAtom Bridge:A Heisenberg Hamiltonian Approach II" Chem.Phys.Lett.
• [Publications] T.Ikoma,K.Akiyama,S.TeroーKubota,and Y.Ikegami: "TimeーResolved EPR Study on the Excited Triplet State of Nonphosphorescent Tropone" J.Phys.Chem.95. 7119-7121 (1991)
• [Publications] K.Akiyama,S.TeroーKubota,and Y.Ikegami: "TimeーResolved EPR Observation of the Shortーlived Excited Triplet States of Diamagnetic Metallophthalocyanines in a Rigid Glassy Matrix" Chem.Phys.Lett.185. 65-67 (1991)
• [Publications] S.TeroーKubota,T.Noguchi,A.Katsuki,K.Akiyama,and Y.Ikegami: "TimeーResolved EPR Spectra of the Excited Triplet States Generated from the Photoinduced Intramolecular Proton Transfer and from the Direct Excitation Reactions in 2ー(NーPhenylacetimidoyl)ー1ーnaphthol" Chem.Phys.Lett.187. 423-426 (1991)
• [Publications] T.Ichikawa and H.Yoshida: "Spatial Distribution of Radicals in GammaーIrradiated Poly(Methyl Methacrylate) Studied by Electron Spin Echo Method" Radiat.Phys.Chem.37. 367-372 (1991)
• [Publications] T.Ichikawa,K.Ueda,and H.Yoshida: "Solvatochromic Shift of Aromatic Ketyl Anions due to Hydrogen Bonding" Bull.Chem.Soc.Jpn.64. 2695-2699 (1991)
• [Publications] T.Okutsu,K.Yano,A.Kawai,and K.Obi: "Dual Spin Polarization of CIDEP in Benzil/Quencher Systems" J.Phys.Chem.95. 5401-5405 (1991)
• [Publications] A.Kawai,T.Okutsu,and K.Obi: "Spin Polarization Generated in the TripletーDoublet Interaction:Hyperfine Dependent CIDEP" J.Phys.Chem.95. 9130-9134 (1991)
• [Publications] A.Kawai and K.Obi: "First Observation of a RadicalーTriplet Pair Mechanism(RTPM) with Doublet Precursor" J.Phys.Chem.96. 52-56 (1992)
• [Publications] S.Yamauchi,T.Ueda,M.Satoh,K.Akiyama,S.TeroーKubota,Y.Ikegami,and M.Iwaizumi: "A TimeーResolved EPR Study on the Photoinduced Electron Transfer Reactions from Metalloporphyrins to Quinones" J.Photochem.Photobiol.
• [Publications] S.Yamauchi,H.Konami,H.Hatano,Y.Ohba,and M.Iwaizumi: "Interplanar Interactions in the Lowest Excited Triplet States of Cofacial Silicon Phthalocyanine μーOxo Polymers Studied by TimeーResolved EPR" J.Phys.Chem.
• [Publications] M.Yagi,B.D.Schlyer,and A.H.Maki: "Optically Detected Magnetic Resonance Study of the Phosphorescent States of transー2,2'ーBipyridine,MetalーFree cisー2,2'ーBipyridine,and [Zn(bpy)]^<2+>" Chem.Phys.157. 209-216 (1991)
• [Publications] M.Yagi,Y.Shioya,and J.Higuchi: "TimeーResolved Electron Paramagnetic Resonance Study of the Triplet States of Nitronaphthalenes" J.Photochem.Photobiol.,Sec.A.62. 65-73 (1991)
• [Publications] M.Yagi,M.Torii,N.Yamauchi,T.Kaneshima,and J.Higuchi: "Effects of Conformation on the Luminescence Properies of 2,2'ーBipyridine and 2,2'ーBiquinoline" Chem.Phys.Lett.187. 604-608 (1991)
• [Publications] H.Murai and K.Kuwata: "CIDEP Study on PhotoーReduction of Xanthone in Alcohols:Novel Indirect Hydrogen Abstraction Steps" J.Phys.Chem.95. 6247-6248 (1991)
• [Publications] H.Murai,Y.Yamamoto,and Y.J.I'Haya: "TimeーResolved ESR Study on Photochemical Formation of Radical Pair in Cyclodextrin Cavities" Can.J.Chem.69. 1643-1648 (1991)
• [Publications] A.Hanazaki,H.Murai,and K.Kuwata: "Photosensitized Triplet State of 1,3ーCyclodienes Detected by a TimeーResolved ESR Method" Chem.Phys.Lett.
• [Publications] H.Yokoi,M.Satoh,and M.Iwaizumi: "Novel Inclusion of Bis(2ーpyridylacarbinolato)copper(II) by Cycloーdextrins" J.Am.Chem.Soc.113. 1530-1533 (1991)
• [Publications] S.Kita,K.Uchida,R.Miyamoto,and M.Iwaizumi: "Proton ENDOR Studies on ZincーDoped Copper(II) Acetate Monohydrate Single Crystal" Bull.Chem.Soc.Jpn.64. 3324-3328 (1991)
• [Publications] M.Hanaya and M.Iwaizumi: "EPR studies of the Paramagnetic Complexes Formed in the Photochemical Reactions of Mo(CO)_6 with oーSemiquinones" J.Org.Chem.401. 31-35 (1991)
• [Publications] T.Kawamura,M.Ebihara,H.Katayama,H.Nishikawa,and T.Yamabe: "Dimer Formation in the Crystal Structure of (Dithiobenzoato)ー(trithioperoxybenzoato)platinum(II):" J.Chem.Soc.,Dalton Trans.2703-2706 (1991)
• [Publications] N.Ishikawa,O.Ohno,and Y.Kaizu: "Hole Delocalization in Naphthalocyaninatophthalocyaninatolutetium(III)." Chem.Phys.Lett.180. 51-56 (1991)
• [Publications] A.B.O'Connell,H.Chandra,S.P.Mishra,A.Hasegawa,and M.C.R.Symons: "Effects of Ionizing Radiation on Cyanamide and Dimethylcyanamide" J.Chem.Soc.,Faraday Trans.87. 3129-3136 (1991)
• [Publications] T.Kato,T.Kodama,M.Oyama,S.Okazaki,T.Shida,T.Nakagawa,Y.Matsui,S.Suzuki,H.Shiromaru,K.Yamauchi,and Y.Achiba: "ESR and Optical Studies of the Radical Anion of C_<60>" Chem.Phys.Lett.186. 35-39 (1991)
• [Publications] T.Shida,T.Kato,T.Momose,and M.Matsushita: "The Insignificance of the Interference of CFCl_2 Radical in the ESR Study of Radical Cations Using the CFCl_3 Matrix" J.Chem.Phys.95. 4725-4726 (1991)
• [Publications] Y.Fujisaka,J.Takahashi,T.Shida,T.Bally,and K.Roth: "Novel Photochemical Reactions of C_8H_<10> Radical Cations" J.Phys.Chem.
• [Publications] K.Toriyama,M.Okazaki and K.Nunome: "ESR Study on the Structure and Dynamics of Propane Cation Radical;The Intrinsic Form with a C_s Symmetry" J.Chem.Phys.95. 3955-3963 (1991)
• [Publications] Y.Tai,M.Okazaki,and K.Toriyama: "ODESR and Fluorescence Study on Geminate Ion Recombination in Low Density Polyethylene doped with Pyrene" J.Chem.Soc,Faraday Trans.88. 23-27 (1992)
• [Publications] M.Okazaki,Y.Tai,K.Nunome,K.Toriyama,and S.Nagakura: "Hyperfineーvs Relaxation Mechanisms of the Magnetic Field Effect on Recombination Fluorescence of Geminate Pairs" Chem.Phys.(1992)
• [Publications] K.Mukai,S.Kikuchi,and M.Nishimura: "StoppedーFlow Investigation of the Reaction of Vitamin C with Tocopheroxyl Radical in Aqueous Triton Xー100 Micelle Solutions.The StructreーActivity Relationship of the Regeneration Reaction of Tocopherol by Vitamin C" J.Biol.Chem.266. 274-278 (1991)
• [Publications] K.Fukuzawa,T.Fujii,and K.Mukai: "PeroxideーDependent and ーIndependent Lipid Peroxidations Catalyzed by Chelated Iron" Arch.Biochem.Biophys.290. 489-496 (1991)
• [Publications] J.Yamauchi,H.Fujita,and Y.Deguchi: "ENDOR and TRIPLE Studies of DiPhenyl Nitroxide(DPNO)" Bull.Chem.Soc.Jpn.64. 3620-3626 (1991)
• [Publications] J.Yamauchi,T.Sugimoto,Y.Arai,M.Sakaguchi,and Z.Yoshida: "Redox Behaviour and Stable Anion Radicals of Cyclic Polycalicenes" J.Chem.Soc.,Perkin Trans.2.
• [Publications] J.Yamauchi,A.Yamaoka,K.Ikemoto,and T.Matsui: "Reaction Mechanism for Ozone Oxidation of Polyethylene as Studied by ESR and IR Spectroscopies" Bull.Chem.Soc.Jpn.64. 1173-1177 (1991)
• [Publications] M.Shiotani,M.Lindgren,N.Ohta,and T.Ichikawa: "Radical cations of cyclohexanes alkylーsubstituted on one carbon:An ESR study of the JahnーTeller sistorted HOMO of cyclohexane" J.Chem.Soc.,Perkin Trans.2. 711-719 (1991)
• [Publications] H.Tachikawa,M.Shiotani,and K.Ohta: "Structure and formation mechanisms of methylーand dimethylacetylene dimer cations:ESR and abーinitio MO studies" J.Phys.Chem.96. 164-171 (1992)
• [Publications] M.Shiotani,K.Komaguti,J.Ohshita,M.Ishikawa,and L.Sjoqvist: "An asymmetrically distorted structure of the 1ーmethylsilacyclohexane radical cation:ESR Evidence" Chem.Phys.Lett.
• [Publications] Y.Kubozono,M.Ata,Y.Suzuki,Y.Gondo and M.Shiotani: "ESR spectra of paraーsubstituted alkylー and alkenylbenzene radical cations in halocarbon matrices" Z.Naturforsch.
• [Publications] 大矢 博昭: "実験化学講座 第9巻「電気・磁気」(編集)" 丸善, 436 (1991)
• [Publications] 工位 武治: "有機磁性材料 第5章 分子性・有機磁性体の応用展望(共著)" シ-エムシ-出版, 21 (1991)