Reaction control by the accerelation and the decerelation of the intersystem crossing by microwave irradiation.

通过微波照射系统间穿越的加速和减速来控制反应。

• 批准号: 07554064
• 负责人: AZUMI Tohru
• 金额: $ 2.75万
• 依托单位: Tohoku University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (A)
• 财政年份: 1995
• 资助国家: 日本
• 起止时间: 1995 至 1996
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-07554064/
• 关键词: radical pair; spin pair; microwave; ADMR; RYDMR; SNP; CIDEP; reaction controll; ESR; 磁場効果; 過渡吸収スペクトル; 過渡吸収検出磁気共鳴法; マイクロ波効果

In this project we have tried to clear the effect of the microwave irradiation on the spin correlation of the radical pair (RP), and to control the photochemical reaction by this effect. For these purpose, we performed the investigation on the following subjects. (1) Construction of the new time-resolved RYDMR (Reaction Yield Detected Magnetic Resonance) and SNP (Stimulate Nuclear Polarization) detection system. For the investigation of the spin correlation of the radical pair, we need a method to observe the spin correlation in fast time resolution (-ns). We apply the various techniques (detection of emission, transient absorption, nuclear polarization, and photo-conductivity) for the observation of the microwave effect on the dynamics of the radical pair. (2) Discussion of the time-resolved ADMR spectra observed in the polymethylene-linked xanthone and xanthene. (3) Observation of the effect of the pulsed microwave on the spin dynamics of RP.(4) The spin dynamics of the RP in the micellar supercage studied by the time-resolved ESR and the stimulated nuclear polarization (SNP) spectra.

本项目试图弄清微波辐射对自由基对自旋关联的影响，并利用这种影响来控制光化学反应。为此，我们对以下主题进行了调查。(1)新的时间分辨RYDMR（反应产率检测磁共振）和SNP（刺激核极化）检测系统的构建。为了研究自由基对的自旋关联，我们需要一种在快时间分辨率（-ns）下观测自旋关联的方法。我们应用各种技术（检测发射，瞬态吸收，核极化，光电导）的观察微波效应的动态的自由基对。(2)在聚亚甲基连接的咕吨酮和咕吨中观察到的时间分辨ADMR光谱的讨论。(3)脉冲微波对快速成形旋转动力学影响的观察。(4)用时间分辨ESR和受激核极化（SNP）谱研究了胶束超笼中RP的自旋动力学。

项目成果

S.S.Ali et al.: "Surprisingly Large Magnetic Field Effect in the Electron-Transfer Reaction of 4,4'-Bipyridine with Triethylamine in Acetonitrile" Chemical Physics Letter. (in press).

S.S.Ali 等人：“乙腈中 4,4-联吡啶与三乙胺的电子转移反应中令人惊讶的大磁场效应”化学物理快报。

S.Kimachi: "Phosphorescence and Zero-Field Optically Detected Magnetic Resonance Studies of (nd)^<10> Transition-Metal Complexes.2." J.Phys.Chem.99. 7242-7245 (1995)

S.Kimachi：“(nd)^<10> 过渡金属配合物的磷光和零场光学检测磁共振研究。2”。

V. F. Tarasov et al.: "Spin-correlated Radical Pairs in Micellar Systems : Mechanism of CIDEP and the Micellar Size Dependence." Chemical Physics. 212. 353-361 (1996)

V. F. Tarasov 等人：“胶束系统中自旋相关的自由基对：CIDEP 机制和胶束尺寸依赖性”。

S. S. Ali et al.: "Surprisingly Large Magnetic Field Effect in the Electron-Transfer Reaction of 4.4'-Bipyridine with Triethylamine in Acetonitrile" Chemical Physics Letter. (in press). (1997)

S. S. Ali 等人：“乙腈中 4.4-联吡啶与三乙胺的电子转移反应中令人惊讶的大磁场效应”化学物理快报。

Y. Yamakage et al.: "Time-resolved DNP measurements of intermediate free radicals created in the photochemical reaction of benzaldehyde. Mechanism of nuclear-polarization creation." Molecular Physics. (in press). (1997)

Y. Yamakage 等人：“苯甲醛光化学反应中产生的中间自由基的时间分辨 DNP 测量。核极化产生的机制。”