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首页> 外文期刊>Applied Magnetic Resonance >Time-resolved EPR spectra of a photoexcited phenanthrene-linked copper(II)-free-base porphyrin dimer: An intermediate-coupling case in a triplet-doublet spin system
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Time-resolved EPR spectra of a photoexcited phenanthrene-linked copper(II)-free-base porphyrin dimer: An intermediate-coupling case in a triplet-doublet spin system

机译：光激发菲连接的无铜卟啉二聚体的时间分辨EPR谱：三重态-双重态自旋系统的中间耦合情况

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Time-resolved electron paramagnetic resonance (TREPR) spectra are presented for a phenanthrene-linked copper(II)-free-base porphyrin dimer. In the lowest electronic excited state, the free-base half is in the (pi, pi*) triplet state and the copper-porphyrin half is in the doublet ground state due to the copper(II) spin. Because of the interaction between the triplet and doublet spins, the excited state of the dimer is described as a coupled friplet-doublet pair state. By choosing the excitation wavelength, this coupled state is produced via either the intersystem crossing within the free base or the energy transfer from the excited state of the copper porphyrin. The observed TREPR spectra show very large spectral widths compared to that of the triplet state in the free-base monomer. In addition, there is a prominent absorptive band in the center of the spectra regardless of the generation pathway. These features can be interpreted as characteristic properties in an intermediate-coupling case, where the degree of the triplet and doublet mixing largely depends on the molecular orientation relative to the magnetic field. [References: 28]
机译：给出了菲连接的无铜卟啉二聚体的时间分辨电子顺磁共振（TREPR）光谱。在最低的电子激发态下，由于铜（II）的自旋，游离碱的一半处于（pi，pi *）三重态，而铜卟啉的一半处于双重基态。由于三线态和双线态自旋之间的相互作用，二聚体的激发态被描述为偶合的小球-双线态对态。通过选择激发波长，可以通过自由碱内的系统间交叉或铜卟啉的激发态的能量转移来产生这种耦合态。与游离碱单体中的三重态相比，观察到的TREPR光谱显示出非常大的光谱宽度。另外，无论产生途径如何，在光谱中心都有明显的吸收带。这些特征可以解释为中间耦合情况下的特性，在这种情况下，三重态和双重态的混合程度很大程度上取决于相对于磁场的分子取向。 [参考：28]

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