分子および分子系の光化学の展開

1992 年度 実績報告書

• 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: 藤嶋 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 / エネルギー移動光反応 / フォトクロミズム / 磁場効果 / 光電気化学 / 電子移動人工蛋白質 / 金属ポリフィリン / 光電変換

研究概要

有機分子の有機化学及び物理化学物研究ではラジクルカチオン転伝反応のエネルギー曲面の解折、フォトクロミック系化合物でもUきい値を持つ系の合成、2分子光反応をするクロメン誘導体の合成と光反応、動起芳香族変化水素から溶存酵素へのエネルギー移動で生ずる一重質酵素生成機構の確立、環境問題とも関連するハロゲン誘導体の脱ハロゲン化反応の機構、アゾ化合物のエネルギー移動及び電子移動反応の研究、赤外部検知でのレーザー光分解装置の作成とそれを利用する金属カルボ=N化合物の光反応の研究、電子移動蛍光消光機構と消光距離の関連、スチルベン誘導体の光量性化に対する磁場効果の研究で大きな成果を得た。有機化学を物理化学系班員との共同研究もあり、この点でも成果を得た。無機・有機金属、錯体の光化学の分野ではアンチモン等高原子価金属を含む金属ポリフィリンを用いた人工光合成物質変検システムの構築、アトワックス掌雑希工類化合物、有機スズ化合物の光化学、金属ポリフィリンに結合された蛋白値の光電子移動反応、光で作られた半導体薄膜の光電気化学、光化学に用いるDNAの選択物切断手法の開発、亜銅ポリフィリンノ光反応性ポリマー係を利用する光ゲート型PHBの開発で茎磁及び応用の両面で大きな成果を得た。分子系の光化学ではゼオライト細孔内に吸着された分子の光動起過程が詳細に研究され細孔内のカチオンの種類が光反応に著しい影響を与える事を明らかにされた。またペリレンを用いたPNヘテロ接合型素子の作製、LB膜の動越エネルギー緩和の研究等でこの分野でも茎磁と応用で大きな成果を得た。超高速および磁気共吸の分野でもヘムト、ピコ秒光反応初期過程の解折、光熱分光法を用いる光反応初期過程の解折、CIONP法による光反応機構の研究で興味ある結果が得られた。

研究成果

• [文献書誌] Y.Takahashi,K.Wakamatsu,S.Morishima,T.Miyashi: "Electron-transfer Photochemistry of Endoperoxides" J.Chem.Soc.Perkin Trans.(1993)
• [文献書誌] H.Ikeda,T.takasaki,Y.TAkahashi,T.Miyashi: "The Radical Gation Cope Rearrangement of 2,5-Dipheny1-1,5-hexadienes under Electron Ionization" J.Chem.Soc.Chem.Commun.(1993)
• [文献書誌] H.Ikeda,T.Oikawa,T.Miyashi: "Substitution Effects on Regioselective Cyclizations of 1,5-and2,4-Diphenyl-1,5-hexadiene Cation Radicals Generatid by the Electron Transfer Photosensitizations" Tetrahedron Lett.(1993)
• [文献書誌] R.Tanaka,I.Suzuki,A.Yamaguchi,H.Misawa,H.Sakuragi,and K.Tokumaru: "Effects of chain length on behavior of biradicals generated from Norrish type I reaction of 2,2-diphenylcycloalkamomes.Isolation and photochemistry of intermediate methylenecyclohexadienyl ketones." Tetrahedron Letters. 33. 3651-3654 (1992)
• [文献書誌] F.Yamaguchi,Y.Kuriyama,H.Sakuragi,and K.Tokumaru: "Electron transfer between neutral radicals generated from photolysis of diphenylmithyl 1-napthalenecarboxlenecarboxylate in polar solvents" Tetrahedron Letters. 33. 5529-5532 (1992)
• [文献書誌] M.Mukai,S.Yamauchi,N.Hirota: "Time-resolved FPR on ghe photochemical reactions of benzil" Journal of Physical Chemistry. 96. 3305-3311 (1992)
• [文献書誌] M.Terazima,N.Hirota: "Population lens in thetmal lens spectroscopy" Journal of Physical Chemistry. 96. 7147-7150 (1992)
• [文献書誌] S.Yamauchi et al.: "Photolysis and pyrolysis of europium compounds in solid and frozen solution systems:Mossbauer and ESR study" Radiochim.Acta.
• [文献書誌] S.Machida,K.Horie,T.Yamashita: "Photon-gated Photchemical Hole Burning by Two-color Sensitization of Photoreactive Polymer via Triplet-triplet inirgy Transfer" Appl.Phys.Lett.,. 60. 286-288 (1992)
• [文献書誌] K.Horie,M.Ikemoto,T.Suzuki,S.Machida,N.Murase: "Frequency Dependence of Quantum Efficiency for Hole Formation in Photochemical Hole-burning for Dye-doped Polymer Systems" Chem.Phys.Lett,. 195. 563-567 (1992)
• [文献書誌] T.Aizawa,et al.: "The Effect of the Coulomb Force on the Diffusional Motion of Radicals as Studied by the Solvent Permittivity Dependence of the CIDNP Intensity." Chemical Physics Letters. 195. 16-20 (1992)
• [文献書誌] Kiminori Maeda,et al.: "Determination of the Exchange Integral by the Low-Field CIDNP in Intramolecular Hydeogen Abstraction Reaction of Polymithylene-Linked Xanthone and Xanthene." The Journal of Physical Chemistry. 96. 4884-4889 (1992)
• [文献書誌] A.Manivannan,H.Hoshi,L.A.Nagahara,A.Fujishiima: "Scanning Prode Microscopic Investigation of of Epitaxially Grown C_<60> Film on MOS_2" Jpn.J.Appl.Phys.31. 3680-3685 (1992)
• [文献書誌] A.Fujishima R.X.Cai K.Hashimoto: "Biochemical Application of Photoelectrochemi-stry:Photokilling of Malignant Cells with Tio_2 Powder" Electrochimica Acta. 18. 153-157 (1993)
• [文献書誌] Seiji Okamoto,Hiroyasu Nishiguchi,Masakazu Anpo: "Phosohorescence and Photochemical Prooerties of Benzophenone Adsorbed on Alkali Cation-Exchanged Zeolite" Chem.Lett.1009-1012 (1992)
• [文献書誌] Masakazu Anpo,Katsuichi Chiba: "Photocatalytic Reduction of CO_2 on Anchoed Titanium Oxides Catalysts" J.Mol.Catal.74. 207-212 (1992)
• [文献書誌] 桑原 克之・宮脇 賢司・那和 一成・野間 直樹・城田 靖彦: "オリゴチオフェン/ペリレン顔料積層薄膜を用いる光電変換" 日本化学会誌. 116-1173 (1992)
• [文献書誌] K.Nishimura,H.Inada,T.Kobata,Y.Matsui,and Y.Shirota: "Hole Drift Mobilities in the Glassy State of Arylaldehyde and Arylketone Hydrazones" Mol.Cryst.lip.Cryst.217. 235-242 (1992)
• [文献書誌] H.Segawa,A.Nakamoto and T.Shimidzu: "Photoinduced Axial Bond Exchange Reaction of Dichloro-phosphorus(V)tetraphenylporphyrin Chloride:Photo-chemical Activation of central 3c-4e Bond" J.Chem.Soc.Chem.Commun.1066-1067 (1992)
• [文献書誌] H.Segawa,R.Azumi,and T.Shimidzu: "Direct Hydroxylation at the Meso Position of Gold(III) Tetraphenylporphyrin by Nucleophilic Addition:Novel Hydroxyphlorin Derivatives" J.Amer.Chem.Soc.,. 114. 7564-7565 (1992)
• [文献書誌] Mamoru Ohashi: "Photoinduced Electron-transfer Reaction of 7-Benzhydry-lidenennorbornene:Chemical Capture of a Radical Cation Intermediate with Nonclassical Cation Character" J.Chem.Soc.,Chem.Commun.1544-1545 (1992)
• [文献書誌] Mamoru Ohashi: "Mass Spectrometry of Carge-transfer Complexes of 7,7^1-8,8^1-Teteacyanoquinodimethane-π-Donor Systems" Organic Mass Spectrometry. 27. 1365-1369 (1992)
• [文献書誌] Kumao Hamanoue et al: "Dechlorination of meso-Substituted Chloroanthracenes (the 9,10-Di-chloro and 9-Chloro Compounds) Via Their Radical Anions Produced by a Diffusion-controlled Reaction of the Lowest Excited Singlet States Dimethylaniline) in Acetonitorile at Room Temperature" J.Phys.Chem.96. 10297-10302 (1992)
• [文献書誌] Kumao Hamanoue et al.: "Reinvestigation of Photocehmical Debromination of 9,10-Dibromoanth-racene and 9-Bromoanthracene by Amine(Triethlamine or N,N-Dimethyl-aniline)Studied by Nanosecond Laser Photolysis in Acetonitrile at Room Temperature" J.Photochem.Photobiol.,A;Chem.69. 305-312 (1993)
• [文献書誌] S.Oishi and T.Kawashima: "Photochemical Behavior of Chlorocarbonylbis(triphenylphosphine)rhodium(I),CIRh(CO)P_2(P=PPh_3).Laser Flash Photolysis with Infrared Deteciton." Chem.Lett.747-750 (1992)
• [文献書誌] S.Oishi,M.Watanabe,and T.Muraishi: "Structure of Transient Cr(CO)_5(phen)Studied by Time-resolved Infrared Spectroscopy" Chem.Lett.
• [文献書誌] Y.Usui,N.Shimizu,S.Mori: "Mechanism on the efficient formation of singlet oxygen by energy transfer from excited singlet and teiplet states of aromatic hydrocarbons" Bull.Chem.Soc.Jpn.,. 65. 897-902 (1992)
• [文献書誌] Y.Usui,S.Takebayashi,M.Takeuchi: "Photochemical nitration of benzoic acid derivatives by irradeation to nitrate ions" Bull.Chem.Soc.Jpn.65. 3183-3185 (1992)
• [文献書誌] H.Kandori,K.Yoshiharo,and S.Tokutomi: "Primary Process of Phytochrome:Initial Step of Photomorphogenesis en Green Plants" The Journal of the American Chemical Society. 114. 10958-10959 (1992)
• [文献書誌] H.Petek,A.J.Bell,and K.Yoshihara: "Fluorescence Excitation Spectra of the SaDtDtレ1aCtDtレ States of Isolated Trienes" The Journal of Chemical Physics. 96. 2412-2415 (1992)
• [文献書誌] 松郷 誠一: "Bis(hydroperoxy)naphthaldiimide as a "Photo-Fenton Reagent":Sequence-specific Photocleavage of DNA" Angew.Chem.Int.Ed.,Engl.,. 30. 1351-1353 (1991)
• [文献書誌] 斉藤 烈: "Photochemistry of Highly Organized Biomolecules:Sequence-selective Photoreaction of DNA" Pure Appl.Chem.64. 305-1310 (1992)
• [文献書誌] N.Ichinose,I.Yamazaki: "Execitation energy relaxation and dimer formation of fluorene in Langmuir-Blodgett monolayer films" Chem.Phys.Lett.,. 197. 364-368 (1992)
• [文献書誌] N.Tamai,H.Matsuo,T.Yamazaki,I.Yamazaki: "Excitation energy relaxation of oxacyanine en Langmuir-Blodgett monolayer films" J.Phys.Chem.96. 6550-6554 (1992)
• [文献書誌] M.Irie,M.Miyatake,K,uchida: "Blocked Photochromism of Diarylethenes" J.Am.Chem.Soc.,. 114. 8715-8716 (1992)
• [文献書誌] M,Irie,K.Sayo: "Solvent Effects on the Photochromic Reactions of Diarylethene Derivatives" J.Phys.Chem.96. 7671-7674 (1992)
• [文献書誌] Y.Takatori,T.Suzuki,Y.KaJii,K.Shibuya,K.Obi: "Highly excited triplte state dynamics of benzophenone studied by pump and probe time-resolved thermal lensing spectroscopy" Chemical.Physics. 169. 291-296 (1993)
• [文献書誌] Y.Kajii,H.itabashi,K.shibuya,K.Obi: "Complex Foration of Benzophenone Ketyl Radical and Teiethylamine" The Journal of Physical Chemistry. 96. 7244-7247 (1992)
• [文献書誌] H.Ikeda,T.Oikawa,and T.Miyashi.: "Subutiution Effects on Regioselective Cyclizations of 1,5-and2,4-Diphenyl-1,5-hixadicene Cation Radicals Generated by the Electron-Transfer-Photosensitizations." Tetrahedron Lett.,1993.
• [文献書誌] H.Ikeda,T.Takasaki,Y.Takahashi,and T.Miyashi.: "The Cation Radical Cope Rearrangement of 2,5-Diphenylhexa-1,5-dienes under Electron Ionization" J.Chem.Soc.Chem.Commun.,1993.
• [文献書誌] Haruo Inoue,Takanobu Okamoto,Masami Komiyama and Mitsuhiko Hida: "Photochemical epoxidation of alkene by visible light in a redox system involving metalloporphyrins and water" J.Photochem.Photobiol.A:Chem.65. 221-227 (1992)
• [文献書誌] Akihide Kitamura et al.: "Intramolecular Triplet Energy Transfer in Ester-Linked Bichromophoric Azoalkanes and Naphthalenes." Journal of Physical Chemistry. 96. 7524-7535 (1992)
• [文献書誌] Takeshi YAMANURA and Hiroki ARAI,: "Tetrakis(thiolato)nickelati(II),[Ni(RS)4]2-: Ligand Dissociation and Electronec Spectra" Bull.Chem.Soc.Jpn.65. 1799-1806 (1992)
• [文献書誌] K.Kikuchi: "A new aspect of photoinduced electron transfer in acetomitrile" J.Photochem.Photobiol.A:Chem.65. 149-156 (1992)
• [文献書誌] Tadashi Okada: "Photoinduced Intramolecular Charge Transfer of TICT and Related Compounds in Femtosecond-Nanosecond Time Regime" Proc.Indian Acad.Sci.(Chem.Sci.). 104. 173-183 (1992)