用辅助体在[Re(L) ((CO) ]复合体中显著改变ILCT生命周期:综合光谱和理论研究
Georgina E Shillito1, Thomas B J Hall1, Dan Preston1
1Department of Chemistry , University of Otago , P.O. Box 56 , Dunedin , New Zealand.
Journal of the American Chemical Society
|March 15, 2018
概括
辅助连接体显著改变复合体的兴奋状态寿命,变化两倍. 这种变化是由能量差距定律解释的,它将非辐射衰变速率与排放能量相关联.
科学领域:
- 无机化学
- 光物理学
- 光谱学
背景情况:
- 在光化学和光物理中,聚复合物至关重要.
- 了解激发状态动力学是设计功能材料的关键.
- 内部电荷转移 (ILCT) 状态影响光物理性质.
研究的目的:
- 研究fac-[Re(L) ((CO) 3 ((α-diimine) ]n+复合物的光物理性质.
- 阐明辅助配体 (L) 在激发状态生命周期中的作用.
- 将兴奋状态行为与电子和结构因素相关联.
主要方法:
- 使用电子和振动光谱 (暂时吸收,发射,TR2,TRIR).
- 使用的量子化学方法 (TDDFT计算).
- 进行了温度依赖的寿命测量.
主要成果:
- 在所有研究的复合物中确定发射状态为3ILCT.
- 观察到3ILCT生命周期 (6. 0μs到27 ns) 的二次变化.
- 发现非辐射衰变率与排放能量之间的相关性, 支持能量差距定律.
结论:
- 辅助连接体选择对激发状态的寿命产生深远的影响,而不会改变激发状态的性质.
- 能量差距法有效地解释了观察到的生命周期变化.
- 这些发现为设计具有定制光物理性质的复合物提供了洞察力.
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