在Bodipy-Perylenebisimide紧二和三中,高效的旋转轨道电荷转移系统间交叉和缓慢的分子内三三能量转移
Xi Chen1, Noreen Rehmat1, Ivan V Kurganskii2
1State Key Laboratory of Fine Chemicals, Frontiers Science Center for Smart Materials, School of Chemical Engineering, Dalian University of Technology, Dalian, 116024, P.R. China.
这项研究探讨了Bodipy-perylenebisimide (BDP-PBI) 二中旋转轨道电荷转移系统间交叉 (SOCT-ISC). 用伊米德替代的BDP-PBI-3显示出高的单氧量子产量,表明有效的SOCT-ISC通路.
科学领域:
- 光化学和光物理学
- 有机电子 有机电子
- 频谱学是一种光谱学.
背景情况:
- 波迪皮 (BDP) 和烯比西米德 (PBI) 是具有独特光物理性质的多功能染色体.
- 了解系统间交叉 (ISC) 机制,特别是旋转轨道电荷转移 ISC (SOCT-ISC),对于开发先进的光电子材料至关重要.
- 单点氧气生成是一个由高效的ISC流程影响的关键应用.
研究的目的:
- 调查SOCT-ISC机制在新的BDP-PBI供体-接受体二和三中.
- 为了将分子结构与光物理性质相关联,包括单片氧量子产量和激发状态动态.
- 阐明不同ISC路径的贡献,例如根对ISC (RP ISC) 和SOCT-ISC.
主要方法:
- 合成BDP-PBI供体-接受体二合体 (BDP-PBI-1,BDP-PBI-3) 和一个三合体 (BDP-PBI-2).
- 秒和纳秒短暂吸收光谱用于研究激发状态动态 (FRET,CS,CR).
- 时间分辨率电子磁共振 (TREPR) 光谱检测ISC机制和旋转极化.
主要成果:
- 与BDP-PBI-1 (30%) 相比,BDP-PBI-3的单氧量子产量 (85%) 显著更高.
- 五秒暂时吸收显示了不同异构体的FRET和CS时间尺度,BDP-PBI-3显示较慢的过程 (40.4 ps FRET,1.55 ns CS).
- TREPR证实了RP ISC和SOCT-ISC的贡献,并观察到RP ISC的罕见 (e, e, e, e, e, e, e, e) 旋转极化.
结论:
- BDP的固定位置显著影响SOCT-ISC的效率和单点氧气生成.
- 在SOCT-ISC路径中,一个上三倍激发状态 (3BDP*) 作为BDP-PBI-3的中间体.
- 无论是RP ISC还是SOCT-ISC机制,都在这些BDP-PBI系统的光物理中发挥着至关重要的作用.
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