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Triplet States Studied by Two-Color Excitation Time-Resolved ESR

通过双色激发时间分辨 ESR 研究三重态

基本信息

批准号：
63430002
负责人：
OBI Kinichi
金额：
$ 17.09万
依托单位：
Tokyo Institute of Technology
依托单位国家：
日本
项目类别：
Grant-in-Aid for General Scientific Research (A)
财政年份：
1988
资助国家：
日本
起止时间：
1988 至 1989
项目状态：
已结题

项目摘要

In this research project, we have carried out four projects using time resolved ESR technique. Results obtained are summarized as follows.(1) Energy Transfer to Higher Triplet State: It is quite difficult to know by the conventional optical spectroscopy what kind of triplet state of energy acceptor is produced in triplet-triplet energy transfer. However, we succeeded to me sure the energy transfer to higher triplet state(T_2) by the time-resolved ESR and to determine the T_2 energy.(2) Spin Polarization Transfer in the Triplet-Doublet Systems: Mechanism of spin polarization transfer was studied in the triplet-doublet systems Using relatively stable radicals as doublet sources. Since the spin polarization transfer occurred when the triplet energy was higher than the excitation energy of radicals, it is. concluded that the spin polarization transfer accompanies energy transfer.(3) Inversion of Spin Polarization in Benzil and alpha-Naphthil:CIDEP generated in the reactions benzil and alpha-naphthyl with aniline and phenol was inverted with time. This is explained by the inversion of spin polarization in the triplet state which is caused by the structural change from non-planar to planar one.(4) Photodissociation of 1-Naphthylmethylchloride: CIDEP spectra of 1-naphthylmethyl radicals was obtained by direct photoexcitation and triplet sensitized reactions of 1-naphthylmethylchloride. It is known from the analysis of CIDEP patterns that 1-naphthylmethylehloride decomposes from the low vibrational level of the lowest triplet state to yield 1-naphthylmethyl radicals and chlorine atoms.

在本研究计划中，我们利用时间分辨ESR技术进行了四个项目。所得结果总结如下。(1)能量转移到更高的三重态：通过常规的光谱学很难知道在三重态-三重态能量转移中产生了哪种能量受体的三重态。然而，我们成功地用时间分辨ESR确定了能量转移到更高的三重态（T_2），并确定了T_2能量。(2)三重态-双重态系统中的自旋极化转移：使用相对稳定的自由基作为双重态源，研究了三重态-双重态系统中的自旋极化转移机制。由于自旋极化转移发生在三重态能量高于自由基的激发能时，因此它是。得出自旋极化转移伴随着能量转移的结论。(3)苯偶酰和α-萘的自旋极化反转：苯偶酰和α-萘与苯胺和苯酚反应产生的CIDEP随时间反转。这是由三重态的自旋极化反转，这是由结构的变化，从非平面到平面之一所造成的解释。(4)1-萘甲基氯的光解离：用1-萘甲基氯的直接光激发和三重态敏化反应获得了1-萘甲基自由基的CIDEP光谱。从CIDEP图谱分析可知，1-萘甲基乙炔从最低三重态的低振动能级分解，生成1-萘甲基自由基和氯原子。