Regulation of Photochemical Reactions by Laser and Magnetic Field

激光和磁场对光化学反应的调控

• 批准号: 03453011
• 负责人: TANIMOTO Yoshifumi
• 金额: $ 4.1万
• 依托单位: HIROSHIMA UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (B)
• 财政年份: 1991
• 资助国家: 日本
• 起止时间: 1991 至 1992
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-03453011/
• 关键词: Magnetic Field Effect; Laser Chemistry; Spin Chemistry; Photochemistry; Transient Absorption; 光化学反応; レ-ザ-化学; 有機光化学

The aim of this project is to develop the novel technique for controlling photochemical reactions by laser and magnetic field.(1) Laser Intensity: The 266 nm laser excitation of &A, &A'-dichloro-o-xylene results in the formation of o-xylylene. From its laser power dependence, it is shown that o-xylylene is generated both one- and two-photon process. (2) Magnetic Field: From the analysis of the magnetic field effect upon the chainlinked singlet and triplet biradicals, its mechanism are precisely clarified. (3) Laser and Magnetic field: In the transient absorption spectra of a bichromophoric chain-linked bisdiazo molecule, magnetic field effect is observed only when the spectra are measured under the intense laser excitation. Upon the intense excitation, a chain-linked biscarbene and a biradical is generated via two-photon process. An external magnetic field affects triplet-singlet intersystem crossing of the biradical generated.In conclusion, the mechanisms of reaction control by laser and magnetic field are clarified.

本课题的目的是开发利用激光和磁场控制光化学反应的新技术。(1)激光强度：266 nm激光激发&A， &A'-二氯-邻二甲苯，生成邻二甲苯。从邻二甲苯的激光功率依赖性来看，邻二甲苯可以单光子和双光子合成。(2)磁场：通过分析磁场对链式单线态和三重态双基的作用，精确地阐明了其作用机理。(3)激光与磁场：在双色聚链双偶氮分子的瞬态吸收光谱中，只有在强激光激发下测量光谱时才会观察到磁场效应。在强激发下，通过双光子过程生成链式比斯卡宾和双自由基。外加磁场影响产生的三重态-单线态系统间交叉。最后，阐明了激光和磁场控制反应的机理。

项目成果

Y.Tanimoto: "Temperature dependence of lifetime of chain-linked biradicals." Chem. Phys. Lett.188. 446-450 (1992)

Y.Tanimoto：“链式双自由基寿命的温度依赖性。”

谷本 能文: "Laser flash photolysis studies of magnetic fiels effects on the hydrogen abstraction of quinoline in micellar solution" Chemical Physics. 162. 7-13 (1991)

Yoshifumi Tanimoto：“磁场对胶束溶液中喹啉夺氢影响的激光闪光光解研究”化学物理，162. 7-13 (1991)。

K.Maeda: "Determination of the exchange integral by the low-field CIDNP in intramolecular hydrogen abstraction of polymethylene-linked xanthone and xanthene." J. Phys. Chem.96. 4884-4889 (1992)

K.Maeda：“通过低场 CIDNP 测定聚亚甲基连接的呫吨酮和呫吨的分子内氢提取中的交换积分。”

前田 公憲: "Determination of the exchange integral by the low-field CIDNP in intramolecular hydrogen abstraction of polymethylene-linked xanthone and xanthene." Journal of Physical Chemistry. 96. 4884-4889 (1992)

Kiminori Maeda：“通过低场 CIDNP 测定聚亚甲基连接的呫吨酮和呫吨的分子内氢提取中的交换积分。”物理化学杂志 96。4884-4889 (1992)

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)

Hiroshi Miyasaka：“乙腈溶液中间隔基连接的二苯胺对二苯甲酮分子内光还原过程的皮秒激光光解研究”化学物理快报 199. 21-28 (1992)。