Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, North Carolina, 27599-3290, USA.
Department of Chemistry, North Carolina State University, Raleigh, North Carolina, 27695, USA.
Photosynth Res. 2022 Feb;151(2):155-161. doi: 10.1007/s11120-021-00859-7. Epub 2021 Jul 14.
The ligand-to-metal charge transfer (LMCT) transitions of [Re(dmpe)] (dmpe = bis-1,2-(dimethylphosphino)ethane) were interrogated using UV/Vis absorbance spectroscopy, photoluminescence spectroscopy, and time-dependent density functional theory. The solvent dependence of the lowest energy charge transfer transition was quantified; no solvatochromism was observed. TD-DFT calculations reveal the dominant LMCT transition is highly symmetric and delocalized involving all phopshine ligand donors in the charge transfer, providing an understanding for the absence of solvatochromism of [Re(dmpe)].
采用紫外-可见吸收光谱、荧光光谱和时间依赖的密度泛函理论研究了[Re(dmpe)]（dmpe=双（1,2-二甲基膦基）乙烷）的配体到金属电荷转移（LMCT）跃迁。定量研究了最低能量电荷转移跃迁的溶剂依赖性；未观察到溶剂变色现象。TD-DFT 计算表明，主导的 LMCT 跃迁具有高度对称性和离域性，涉及电荷转移中的所有膦配体供体，这为[Re(dmpe)]缺乏溶剂变色现象提供了理解。
