Characterizing Ultrafast Intersystem Crossing Pathways in Molecular Pt Dimers Using Time-Resolved Wide-Angle X-ray Scattering

IF 4.6 2区化学 Q2 CHEMISTRY, PHYSICAL

The Journal of Physical Chemistry Letters Pub Date : 2025-07-03 DOI:10.1021/acs.jpclett.5c01245

Michael W. Mara*, Denis Leshchev, Nicholas P. Weingartz, Arnold M. Chan, Adam K. Nijhawan, Andrew J. S. Valentine, Xiaolin Liu, Sarah Kromer, Darren Hsu, Pyosang Kim, Elisa Biasin, Timothy Brandt van Driel, Felix N. Castellano*, Xiaosong Li* and Lin X. Chen*,

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Abstract

Vibronic coupling between transition metal charge transfer states is a potential mechanism for enhancing the intersystem crossing (ISC) rate. Vibronic coupling-driven ISC has been observed in Pt(II) dimer complexes, where the trajectory across excited-state pathways is tuned by atomic displacements via Pt–Pt stretching vibrations. Time-resolved wide-angle X-ray scattering (TR-WAXS) was utilized to quantify the Pt–Pt contraction following metal–metal-to-ligand charge transfer (MMLCT) excitation in Pt dimers with different bridging ligands. Both complexes exhibit Pt–Pt bond formation with a decrease in Pt–Pt distance of ∼ 0.25 Å and coherent vibrational wavepackets (CVWPs) encoded in the Pt–Pt contraction of both dimers. However, the complexes exhibit different time-dependent evolution of their CVWPs. Analysis of interference patterns between different CVWPs is used to track the trajectory across the excited-state surfaces. This work demonstrates that the interference between CVWPs in ultrafast TR-WAXS encodes indirect information regarding electronic excited-states to reveal the Pt dimer bridge-dependent ISC mechanism.

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用时间分辨广角x射线散射表征分子铂二聚体的超快系统间交叉途径。

过渡金属电荷转移态之间的振动耦合是提高系统间交叉（ISC）速率的潜在机制。在Pt（II）二聚体配合物中已经观察到振动耦合驱动的ISC，其中通过Pt-Pt拉伸振动的原子位移调节激发态路径的轨迹。利用时间分辨广角x射线散射（TR-WAXS）量化了不同桥接配体的铂二聚体中金属-金属-配体电荷转移（MMLCT）激发后的Pt-Pt收缩。这两种配合物都表现出Pt-Pt键形成，Pt-Pt距离减少了~ 0.25 Å，并且在两种二聚体的Pt-Pt收缩中编码了相干振动波包（CVWPs）。然而，复合物的CVWPs表现出不同的随时间变化。通过分析不同CVWPs之间的干涉模式来跟踪激发态表面的轨迹。这项工作表明，在超快TR-WAXS中，CVWPs之间的干扰编码了有关电子激发态的间接信息，揭示了Pt二聚体桥依赖的ISC机制。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

The Journal of Physical Chemistry Letters CHEMISTRY, PHYSICAL-NANOSCIENCE & NANOTECHNOLOGY

CiteScore

9.60

自引率

7.00%

发文量

1519

审稿时长

1.6 months

期刊介绍： The Journal of Physical Chemistry (JPC) Letters is devoted to reporting new and original experimental and theoretical basic research of interest to physical chemists, biophysical chemists, chemical physicists, physicists, material scientists, and engineers. An important criterion for acceptance is that the paper reports a significant scientific advance and/or physical insight such that rapid publication is essential. Two issues of JPC Letters are published each month.