基于Zr的金属有机框架中的激发状态电子属性作为拓网络的函数
Jierui Yu1, JaeHong Park2, Andrea Van Wyk1
1Department of Chemistry and Biochemistry , Southern Illinois University , 1245 Lincoln Drive , Carbondale , Illinois 62901 , United States.
Journal of the American Chemical Society
|July 25, 2018
概括
金属有机框架 (MOF) 的拓结构对它们的光采集性能产生重大影响. 不同的网络结构影响激发状态激发子的行为和能量转换,对于先进的材料应用至关重要.
科学领域:
- 材料科学
- 化学学
- 物理
背景情况:
- 金属有机框架 (MOF) 模仿自然光采集系统进行能量转换.
- 了解MOF拓与激发状态属性之间的联系对于优化能源应用至关重要.
研究的目的:
- 研究基于Zr(IV) 的MOF的拓差异如何影响它们的兴奋状态电子结构.
- 将拓网络与激子移位和能量转换途径相关联.
主要方法:
- 在模型化合物上使用时间依赖密度函数理论 (TD-DFT) 的计算分析.
- 光学表征包括秒瞬时吸收 (fs-TA) 和光谱.
- 两个MOF的比较 (NU-901和NU-1000) 具有相同的链接器但不同的拓.
主要成果:
- 在光学上相关的激发状态 (S1,S2,Sn) 在多个链接器 (高达1.7 nm) 上被移位.
- 形成极性激子,其振荡强度取决于拓网络和染色体间相互作用.
- 通过S1 → Sn转换,NU-901表现出超快速的分离体形成 (τ = 2 ps),NU-1000和自由链接体中没有这种现象.
结论:
- 连接器的拓布局对MOF中的兴奋状态电子结构和动态进行了关键控制.
- 拓差异决定了激子的行为,影响了能量转换效率.
- 在NU-901中观察到的快速排卵体形成突出了特定拓网对激发状态过程的影响.
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