Chemical transformations in charge transfer states result from the interplay between electronic dynamics and nuclear reorganization along excited-state trajectories. Here, we investigate the ultrafast structural dynamics following photoinduced electron transfer from the metal–metal-to-ligand charge transfer state of an electron donor, a Pt dimer complex, to a covalently linked electron acceptor group using ultrafast time-resolved wide-angle X-ray scattering and optical transient absorption spectroscopy methods to disentangle the interdependence of the excited-state electronic and nuclear dynamics. Following photoexcitation, Pt–Pt bond formation and contraction takes up to 1 ps, much slower than the corresponding process in analogous complexes without electron acceptor groups. Because the Pt–Pt distance change is slow with respect to excited-state electron transfer, it can affect the rate of electron transfer. These results have potential impacts on controlling electron transfer rates via structural alterations to the electron donor group, tuning the charge transfer driving force.

中文翻译：

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从超快电子和核运动的角度解读过渡金属配合物中的电荷转移过程

电荷转移态的化学转变是电子动力学和沿激发态轨迹的核重组之间相互作用的结果。在这里，我们使用超快时间分辨广角X光研究了光诱导电子从电子供体（Pt二聚体复合物）的金属-金属-配体电荷转移状态转移到共价连接的电子受体基团后的超快结构动力学射线散射和光学瞬态吸收光谱方法可以解开激发态电子和核动力学的相互依赖性。光激发后，Pt-Pt 键的形成和收缩需要 1 ps，比没有电子受体基团的类似配合物中的相应过程慢得多。由于 Pt-Pt 距离变化相对于激发态电子转移来说很慢，因此它会影响电子转移速率。这些结果对通过电子供体基团的结构改变来控制电子转移速率、调节电荷转移驱动力具有潜在影响。