Research of Physical Chemistry on Activity and Spin-Spin Interaction of Paramagnetic Molecular Species

顺磁性分子活性和自旋-自旋相互作用的物理化学研究

• 批准号: 02303001
• 负责人: HIGUCHI Jiro
• 金额: $ 6.02万
• 依托单位: Yokohama National University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Co-operative Research (A)
• 财政年份: 1990
• 资助国家: 日本
• 起止时间: 1990 至 1992
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-02303001/
• 关键词: EPR; Radical; CIDEP; Spin Chemistry; Metal Complex; Lowest Excited Triplet State; Spin Polarization; Relaxation Rate; 常磁性種; フリーラジカル; 励起三重項状態; EPR(ESR); 時間分解EPR; スピン間相互作用; フリ-ラジカル; ESR; 時間分解ESR; ENDOR

Recently, the lnvestigations of paramagnetic molecolar species, lncluding excited molecules, make rapid progress by improving the experimental techniques.Under such circumstances, the present co-operative research was undertaken. The main purpose of this is the establishment of the research system which makes possible to investirate the special characters on the electronic structure of each molecular species, from both the theoretical and the experimental viewpoints. By reexaming the experimental informations and the theoretical considerations, the fundamental parts in the research system of paramagnetic molecular species could be understood by focussing the reactivity, the dynamic behavior, and the spin-spin-interaction. Thus, the development of our research becomes with great possibilities in the near future. The present co-operative research group with nineteen investigators began to take charge of the following four partial subjects; (1) the improvement of chemical method for param … More agnetic molecular species in focussing the time-resolved and the frequency-resolved methods. (2) the problems on the spin-spin interaction of paramagnetic species produced in the excited state. (3) the reactivity and the spin-spin interaction of metal complexes, and (4) the reactivity of free radicals trapped in condensed phases. After that, the complete resolutions of the present problems were obtained in close co-operation among all the member of our group by the exchange of information and the mutual discussions. As a result, many fruitful investigations and internationally high-level papers have been published. The main partial subjects of these are described as follows: Development of quantitative analysis of CIDEP signals, taking the diffusion process into consideration; Methodologycal development for the purpose of completing the spin chemistry; Determination of molecular structure, dynamic behavior, and energy-transfer rate between the same molecular species; Detection of spin polarizalion produced in the ground state of metal complexes after photoexcitation; Evidence for unsymmetrical structure of o-cation radicals of linear alkanes; Evidence for the correlation between the rate of hydrogen-atom-abstraction from n-alkanes and the relaxation rate of their C-C bending vibralion. detected by the pulse EPR method. Less

近年来，随着实验技术的不断完善，包括激发态分子在内的顺磁性分子种类的研究取得了长足的进展。在这种情况下，进行了目前的合作研究。这样做的主要目的是建立一个研究体系，使我们能够从理论和实验两个角度来研究每个分子物种的电子结构的特殊性。通过对实验信息和理论考虑的重新审视，顺磁性分子物种研究体系的基本部分可以通过聚焦反应性、动力学行为和自旋-自旋相互作用来理解。因此，在不久的将来，我们的研究发展具有很大的可能性。目前的合作课题组有19名研究人员，开始负责以下四个部分课题；(1)化学方法在时间分辨方法和频率分辨方法上的改进，增加了磁性分子种类。(2)激发态产生的顺磁物质自旋相互作用问题。(3)金属配合物的反应性和自旋-自旋相互作用；(4)被困在凝聚相中的自由基的反应性。此后，在我们小组所有成员的密切合作下，通过交换信息和相互讨论，全面解决了目前的问题。因此，发表了许多卓有成效的研究和具有国际水平的论文。其中主要的部分课题描述如下：考虑扩散过程的CIDEP信号定量分析的发展；完成自旋化学的方法发展；确定分子结构、动力学行为和相同分子物种之间的能量转移率；光激发后金属配合物基态自旋极化的检测线性烷烃o阳离子自由基不对称结构的证据正构烷烃的氢原子抽离速率与其C-C弯曲振动的弛豫速率之间的相关性证据。用脉冲EPR法检测。少

项目成果

T. Ikoma, K. Akiyama, S. Tero-Kubota, and Y. Ikegami: "Structural Effects on the Radiationless Transition from the T, States of Tropone Derivatives" J. Phys. Chem.97. 303-305 (1993)

T. Ikoma、K. Akiyama、S. Tero-Kubota 和 Y. Ikegami：“对托酮衍生物 T 态无辐射转变的结构效应”J. Phys。

T. Otuka, A. Sekine, Y. Ohashi, and Y. Kaizu: "The Crystal Water Affecting ^2E_g*^4A_<20> Relaxation in Tris(oxalato)chromate(III) Complexes" Bull. Chem. Soc. Jpn.65. 3378-3385 (1992)

T. Otuka、A. Sekine、Y. Ohashi 和 Y. Kaizu：“结晶水影响 Tris(oxalato)chromate(III) 复合物中的 ^2E_g*^4A_<20> 弛豫”公牛。

K.Toriyama and H.Okazaki: "Selectively Weakened C-C σ-Bond in Cation Radicals of Linear and Branched Pentanes as Studies by Electron Spin Resonance" J. Phys. Chem.96. 6986-6991 (1992)

K.Toriyama 和 H.Okazaki：“通过电子自旋共振研究选择性减弱直链和支链戊烷阳离子自由基中的 C-C σ-键”J. Phys. 6986-6991 (1992)。

T.Ichikawa and II.Yoshida: "Selectivity of Alkyl Radical Formation from Branched Alkanes Studied by Electron Spin Resonace and Electron Spin Echo Spectroscopy" J. Phys. Chem.96. 7656-7661 (1992)

T.Ichikawa 和 II.Yoshida：“通过电子自旋共振和电子自旋回波光谱研究支链烷烃中烷基自由基形成的选择性”J. Phys。

Y.Fujisaka, J.Takahashi, T.Shida, T.Bally, and K.Roth: "Novel Photochemical Reaction of C_BII_<10> RAdical Cations" J. Phys. Chem.96. 2205-2210 (1992)

Y.Fujisaka、J.Takahashi、T.Shida、T.Bally 和 K.Roth：“C_BII_<10> 自由基阳离子的新型光化学反应”J. Phys。