新的连接体设计提供了移位,并促进了在Ru (II) 复合体中整个可见区域的强度吸收
Tyler J Whittemore1, Travis A White1, Claudia Turro1
1Department of Chemistry and Biochemistry, The Ohio State University , Columbus, Ohio 43210, United States.
Journal of the American Chemical Society
|December 21, 2017
概括
一个新的鲁复合物,Ru-qdpq,表现出红移吸收和长期活跃状态,与相关复合物不同. 这一发现为开发太阳能和光化疗的先进材料提供了途径.
科学领域:
- 协调化学
- 光物理学
- 材料科学
背景情况:
- (II) 复合物与含有多和的配体对于光采集和能量转换应用至关重要.
- 了解激发状态动力学和电子通信是调整它们的光物理性质的关键.
研究的目的:
- 为了合成和表征一种新的Ru(II) - antraquinone复合物, [Ru(bpy) 2(qdpq) ]
- 调查Ru-qdpq与相关复合体Ru-qdppz的光物理特性,特别是激发状态寿命和吸收光谱.
- 阐明联体协调模式在决定电子通信和兴奋状态行为的作用.
主要方法:
- 合成和表征Ru-qdpq和Ru-qdppz复合物
- 稳态吸收光谱测定吸收最大值和光谱变化.
- 超快速光谱和时间解析测量以分析激发状态的动态和寿命.
- 电化学和密度功能理论 (DFT) 计算以探测电子结构和属性.
主要成果:
- 与Ru-qdppz (λmax = 450 nm) 相比,Ru-qdpq在546nm处显示出强烈的MLCT吸收.
- 鲁-qdpq表现出长寿命的 (τ = 19 ns) MLCT激发状态,其电子密度在qdpq连接体上脱局.
- 由于联体内的电子隔离状态,Ru-qdppz显示了寿命较短的激发状态 (τ = 362 ps).
结论:
- qdpq和qdppz联体的独特协调导致不同的电子通讯路径,影响激发状态和电子转移特性.
- Ru-qdpq的红移吸收和长寿命激发状态为开发新材料提供了一个有希望的平台.
- 这些发现为设计可调节光物理性质的复合物铺平了道路,用于太阳能转化和光化疗.
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