1992 Fiscal Year Annual Research Report

分子磁性による反応制御

Research Project

Project/Area Number	04242107
Research Institution	The Institute of Physical and Chemical Research
Principal Investigator	林久治理化学研究所, 分子光化学研究室, 主任研究員 (50087508)
Co-Investigator(Kenkyū-buntansha)	住谷実静岡理工科大学, 理工学部, 助教授 (20201585) 中垣良一金沢大学, 薬学部, 助教授 (20159057) 泰憲典青山学院大学, 理工学部, 教授 (80082741) 谷本能文広島大学, 理学部, 助教授 (10110743)
Keywords	外部磁場効果 / レーザー閃光法 / ラジカル対 / 超伝導磁石 / フェニルカルベン / 不斉誘導 / 光学活性カルボン酸 / 磁場消光
Research Abstract	本研究班の研究目的は、外部磁場効果や磁気同位体効果などの、分子磁性による反応制御がどのような新しい反応系に拡張できるかを追求することにある。研究代表者および研究分担者の本年度の研究実績は次の通りである。林は第3周期以上の原子上に不対電子が存在する重原子ラジカルの液相反応における磁場効果を見いだすことを目的として、ナノ秒レーザー閃光法と電磁石を用いて、三重項状態を経由する光解離反応や光電子移動反応において、S-ラジカル、Si-ラジカル、およびGe-ラジカルを含むラジカル対の寿命や散逸ラジカルの収量が磁場で増加することを見いだした。しかし、1.35Tの磁場による変化量は50%以下であるので、超伝導磁石を用いた0-10T領域の測定を開始している。谷本は高スピン状態(S≧1)にある化合物の液本反応において磁場効果を見いだすことを目的として、レーザー閃光法と電磁石を用い、メチレン鎖の両端に2ケのフェニルカルベンや励起三重項状態を生成した系の磁場効果を測定した。前者には磁場効果が観測されなかったが、後者では三重項状態の半減期が0.7Tの磁場により10%増加した。また、パルス磁石を用いた0-20T領域の測定を開始している。秦と中垣は液相化学反応における左右対称性の破れや磁場による不斉誘導を研究する目的で、アザ芳香族と各種の光学活性カルボン酸との光化学反応における反応生成物の磁場効果、溶媒効果、および蛍光消光にS-体とR-体で顕緒な差を観測した(秦)。また、これらの反応系のメチレン鎖連結系を合成し、分子内光反応を定常光照射法とレーザー閃光法を用いた研究を推進している(中垣)。気相反応の磁場効果に関しては、体系的理解がまだ完成していないので、住谷は気相反応の磁場効果の機構を解明する目的で、NOのB^2Π-X^2Π発光に対する磁場消光を研究した。B^2Π状態の各振動状態へLIF法で直接励起した際の蛍光には磁場効果がなく、B^2Π状態が生成するまでの過程が磁場の影響を受けるものと考えられる。

Research Products

(14 results)

All Other

All Publications (14 results)

[Publications] 坂口喜生: "Internal Magnetic Fiels Effect of Transition Metal Ions on the Photochemical Reaction of Naphthoquinone in Micelles" Chemical Physics. 161. 119-129 (1992)
[Publications] 藤村勇一: "Mechanism of External Magnetic Field Dependent Fluorescence Decays of Gaseous Carbon Disulfide" Chemical Physics. 161. 205-212 (1992)
[Publications] 阿部晴雄: "External Magnetic Field Effects on Chemiluminescence from C_2(d)and CN(B) States in Low Pressure C_2H_2/N,O Flames" Chemical Physics. 161. 225-234 (1992)
[Publications] 若狭雅信: "The First Direct Observation of Magnetic Field Effects on the Dynamic Behavior of Radical Pairs Involving Group 14 Silicon Germanium Centered Radicals" The Journal of The American Chemical Society. 114. 8171-8176 (1992)
[Publications] 若狭雅信: "Magnetic Field Effects on the Photoinduced Electron-Transfer Reactions between Hexamethyldisilane and Aromatic Nitriles in Brij 35 Micellar Solutions" The Journal of Physical Chemistry. 96. 9651-9656 (1992)
[Publications] 若狭雅信: "Magnetic Field Effect on the Photodecomposition of p-Aminophenyl Disulfide in a Micellar Solution" The Journal of Physical Chemistry. 97. (1993)
[Publications] 谷本能文: "Laser Flash Photolysis Studies of Magnetic Field Effects on the Hydrogen Abstraction Reaction of Quinoline in Micellar Solution" Chemical Physics. 162. 7-13 (1992)
[Publications] 前田公憲: "Determination of the Exchange Integral by the Low-Field CIDNP in Intramolecular Hydrogen Abrstaction of Polymethylene-Linked Xanthone and Xanthene" The Journal of Physical Chemistry. 96. 4884-4889 (1992)
[Publications] 谷本能文: "Temperature Dependence of Lifetime of Chain-Linked Biradicals" Chemical Physics Letters. 188. 446-450 (1992)
[Publications] 宮坂博: "Picosecond Laser Photolysis Studies on the Intramolecular Photoreduction Process of Benzophenone by Diphenylamine Linked by Spacers in Acetonitrile Solution" Chemical Physics Letters. 199. 21-28 (1992)
[Publications] 谷本能文: "Mechanism of the Magnetic Field Effects on the Decay Rate of Chain-Linked Biradicals" The Journal of Physical Chemirtry. 96. 9844-9846 (1992)
[Publications] 秦憲典: "Photochemical Reaction of 4-Methy1-2-quinolinecarbonitrile with optically active (S)-or (R)-2-Phenylpropionic Acid.The Magnetic-Field and Solvent Effects and Chial-Symmetry Breaking" Chemical Physics. 162. 47-52 (1992)
[Publications] 秦憲典: "Photochemical Reactions of 4-Methy1-2-quinolinecarbonitrile with 2,2-Diphenylalkanoic Acids.The Magnetic-Field and Solvent Effects ans Reaction Mechanism." Bulletin of The Chemical Society of Japan. 66. (1993)
[Publications] 内藤和彦: "Intermediates for Photoisomerization of Butenylnaphthalene in the Presence of Electron Acceptors as Studied by Solvent Dependencs of Magnetic Field Effects." Chemistry Letters. 1077-1080 (1992)

1992 Fiscal Year Annual Research Report

分子磁性による反応制御

Principal Investigator

林 久治 理化学研究所, 分子光化学研究室, 主任研究員 (50087508)

Research Products

[Publications] 坂口 喜生: "Internal Magnetic Fiels Effect of Transition Metal Ions on the Photochemical Reaction of Naphthoquinone in Micelles" Chemical Physics. 161. 119-129 (1992)

[Publications] 藤村 勇一: "Mechanism of External Magnetic Field Dependent Fluorescence Decays of Gaseous Carbon Disulfide" Chemical Physics. 161. 205-212 (1992)

[Publications] 阿部 晴雄: "External Magnetic Field Effects on Chemiluminescence from C_2(d)and CN(B) States in Low Pressure C_2H_2/N,O Flames" Chemical Physics. 161. 225-234 (1992)

[Publications] 若狭 雅信: "The First Direct Observation of Magnetic Field Effects on the Dynamic Behavior of Radical Pairs Involving Group 14 Silicon Germanium Centered Radicals" The Journal of The American Chemical Society. 114. 8171-8176 (1992)

[Publications] 若狭 雅信: "Magnetic Field Effects on the Photoinduced Electron-Transfer Reactions between Hexamethyldisilane and Aromatic Nitriles in Brij 35 Micellar Solutions" The Journal of Physical Chemistry. 96. 9651-9656 (1992)

[Publications] 若狭 雅信: "Magnetic Field Effect on the Photodecomposition of p-Aminophenyl Disulfide in a Micellar Solution" The Journal of Physical Chemistry. 97. (1993)

[Publications] 谷本 能文: "Laser Flash Photolysis Studies of Magnetic Field Effects on the Hydrogen Abstraction Reaction of Quinoline in Micellar Solution" Chemical Physics. 162. 7-13 (1992)

[Publications] 前田 公憲: "Determination of the Exchange Integral by the Low-Field CIDNP in Intramolecular Hydrogen Abrstaction of Polymethylene-Linked Xanthone and Xanthene" The Journal of Physical Chemistry. 96. 4884-4889 (1992)

[Publications] 谷本 能文: "Temperature Dependence of Lifetime of Chain-Linked Biradicals" Chemical Physics Letters. 188. 446-450 (1992)

[Publications] 宮坂 博: "Picosecond Laser Photolysis Studies on the Intramolecular Photoreduction Process of Benzophenone by Diphenylamine Linked by Spacers in Acetonitrile Solution" Chemical Physics Letters. 199. 21-28 (1992)

[Publications] 谷本 能文: "Mechanism of the Magnetic Field Effects on the Decay Rate of Chain-Linked Biradicals" The Journal of Physical Chemirtry. 96. 9844-9846 (1992)

[Publications] 秦 憲典: "Photochemical Reaction of 4-Methy1-2-quinolinecarbonitrile with optically active (S)-or (R)-2-Phenylpropionic Acid.The Magnetic-Field and Solvent Effects and Chial-Symmetry Breaking" Chemical Physics. 162. 47-52 (1992)

[Publications] 秦 憲典: "Photochemical Reactions of 4-Methy1-2-quinolinecarbonitrile with 2,2-Diphenylalkanoic Acids.The Magnetic-Field and Solvent Effects ans Reaction Mechanism." Bulletin of The Chemical Society of Japan. 66. (1993)

[Publications] 内藤 和彦: "Intermediates for Photoisomerization of Butenylnaphthalene in the Presence of Electron Acceptors as Studied by Solvent Dependencs of Magnetic Field Effects." Chemistry Letters. 1077-1080 (1992)

林久治理化学研究所, 分子光化学研究室, 主任研究員 (50087508)

[Publications] 坂口喜生: "Internal Magnetic Fiels Effect of Transition Metal Ions on the Photochemical Reaction of Naphthoquinone in Micelles" Chemical Physics. 161. 119-129 (1992)

[Publications] 藤村勇一: "Mechanism of External Magnetic Field Dependent Fluorescence Decays of Gaseous Carbon Disulfide" Chemical Physics. 161. 205-212 (1992)

[Publications] 阿部晴雄: "External Magnetic Field Effects on Chemiluminescence from C_2(d)and CN(B) States in Low Pressure C_2H_2/N,O Flames" Chemical Physics. 161. 225-234 (1992)

[Publications] 若狭雅信: "The First Direct Observation of Magnetic Field Effects on the Dynamic Behavior of Radical Pairs Involving Group 14 Silicon Germanium Centered Radicals" The Journal of The American Chemical Society. 114. 8171-8176 (1992)

[Publications] 若狭雅信: "Magnetic Field Effects on the Photoinduced Electron-Transfer Reactions between Hexamethyldisilane and Aromatic Nitriles in Brij 35 Micellar Solutions" The Journal of Physical Chemistry. 96. 9651-9656 (1992)

[Publications] 若狭雅信: "Magnetic Field Effect on the Photodecomposition of p-Aminophenyl Disulfide in a Micellar Solution" The Journal of Physical Chemistry. 97. (1993)

[Publications] 谷本能文: "Laser Flash Photolysis Studies of Magnetic Field Effects on the Hydrogen Abstraction Reaction of Quinoline in Micellar Solution" Chemical Physics. 162. 7-13 (1992)

[Publications] 前田公憲: "Determination of the Exchange Integral by the Low-Field CIDNP in Intramolecular Hydrogen Abrstaction of Polymethylene-Linked Xanthone and Xanthene" The Journal of Physical Chemistry. 96. 4884-4889 (1992)

[Publications] 谷本能文: "Temperature Dependence of Lifetime of Chain-Linked Biradicals" Chemical Physics Letters. 188. 446-450 (1992)

[Publications] 宮坂博: "Picosecond Laser Photolysis Studies on the Intramolecular Photoreduction Process of Benzophenone by Diphenylamine Linked by Spacers in Acetonitrile Solution" Chemical Physics Letters. 199. 21-28 (1992)

[Publications] 谷本能文: "Mechanism of the Magnetic Field Effects on the Decay Rate of Chain-Linked Biradicals" The Journal of Physical Chemirtry. 96. 9844-9846 (1992)

[Publications] 秦憲典: "Photochemical Reaction of 4-Methy1-2-quinolinecarbonitrile with optically active (S)-or (R)-2-Phenylpropionic Acid.The Magnetic-Field and Solvent Effects and Chial-Symmetry Breaking" Chemical Physics. 162. 47-52 (1992)

[Publications] 秦憲典: "Photochemical Reactions of 4-Methy1-2-quinolinecarbonitrile with 2,2-Diphenylalkanoic Acids.The Magnetic-Field and Solvent Effects ans Reaction Mechanism." Bulletin of The Chemical Society of Japan. 66. (1993)

[Publications] 内藤和彦: "Intermediates for Photoisomerization of Butenylnaphthalene in the Presence of Electron Acceptors as Studied by Solvent Dependencs of Magnetic Field Effects." Chemistry Letters. 1077-1080 (1992)