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首页> 外文期刊>Physical chemistry chemical physics: PCCP >Dual electron transfer pathways from the excited C-60 radical anion: enhanced reactivities due to the photoexcitation of reaction intermediates
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Dual electron transfer pathways from the excited C-60 radical anion: enhanced reactivities due to the photoexcitation of reaction intermediates

机译：来自激发的C-60自由基阴离子的双电子转移途径：由于反应中间体的光激发而提高了反应性

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In the present study, electron transfer (ET) processes from excited radical anions have been investigated using dyad molecules including C-60. The deactivation process of excited C-60(center dot-), including the internal conversion from the D-1 to the D-0 state and the cooling process of the vibrationally hot ground state (D-0(hot)), was observed spectroscopically for the first time. These processes could be unambiguously distinguished by the observation of the stimulated emission from the D-1 state. The intramolecular ET processes from the excited C-60(center dot) were confirmed by the transient absorption spectra. Clearly, both D-1 and D-0(hot) states acted as precursors for the ET, i.e., dual ET pathways were confirmed. The driving force dependence of the ET rates was well characterized by the Marcus theory, which revealed that the forward ET processes are located at the top region of the Marcus parabola. In addition, the ET from the excited imide radical anion to C-60 and that from the ground state C-60(center dot-) to imide were examined. The ET rate from the excited imide radical anion and that from ground state C-60(center dot-) did not follow the Marcus parabola estimated for the ET from the excited C-60(center dot-). The observed difference can be attributed to the difference in the energy required to form the reduced spacer (Delta) in the superexchange mechanism. Because the Delta value tends to become smaller for ET processes from excited radical ions, fast and efficient ET processes are expected from these states as demonstrated in the present study.
机译：在本研究中，已使用包括C-60在内的二元分子研究了从激发的自由基阴离子产生的电子转移（ET）过程。观察到激发的C-60（中心点）的失活过程，包括从D-1到D-0状态的内部转换以及振动热基态（D-0（热））的冷却过程。首次进行光谱分析。通过观察来自D-1状态的受激发射，可以清楚地区分这些过程。瞬态吸收光谱证实了激发的C-60（中心点）的分子内ET过程。显然，D-1和D-0（热）状态均充当ET的前体，即，证实了双ET途径。马库斯理论很好地表征了ET速率对驱动力的依赖性，该理论揭示了正向ET过程位于抛物线Marcus的顶部。另外，还研究了从激发的酰亚胺基自由基阴离子到C-60的ET和从基态C-60（中心点）到酰亚胺的ET。激发的酰亚胺自由基阴离子和基态C-60（中心点）的ET速率不遵循Marcus抛物线估计的C-60（中心点）的ET。观察到的差异可以归因于在超级交换机构中形成减小的间隔物所需的能量差异。由于从激发的自由基离子到ET过程的Delta值趋于变小，因此如本研究所示，从这些状态可以期望快速而有效的ET过程。

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