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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Probing the photoexcited states of rhodium corroles by time-resolved Q-Band EPR. Observation of strong spin-orbit coupling effects
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Probing the photoexcited states of rhodium corroles by time-resolved Q-Band EPR. Observation of strong spin-orbit coupling effects

机译：通过时间分辨Q波段EPR探测铑的光激发态。观察强自旋轨道耦合效应

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摘要

The photoexcited states of two 5,10,15-tris(pentafluorophenyl)corroles (tpfc), hosting Rh(III) in their core, namely Rh(pyr)(PPh3)(tpfc) and Rh(PPh3)(tpfc), have been studied by time-resolved electron paramagnetic resonance (TREPR) combined with pulsed laser excitation. Using the transient nutation technique, the spin polarized spectra are assigned to photoexcited triplet states. The spectral widths observed for the two Rh(III) corroles crucially depend on the axial ligands at the Rh(III) metal ion. In case of Rh(PPh3)(tpfc) the TREPR spectra are found to extend over 200 mT, which exceeds the spectral width of non-transition-metal corroles by more than a factor of 3. Moreover, the EPR lines of the Rh(III) corroles are less symmetric than those of the non-transition-metal corrroles. The peculiarities in the TREPR spectra of the Rh(III) corroles can be rationalized in terms of strong spin-orbit coupling (SOC) associated with the transition-metal character of the Rh(III) ion. It is assumed that SOC in the photoexcited Rh(III) corroles effectively admixes metal centered (3)dd-states to the corrole centered (3)pi pi*-states detected in the TREPR experiments. This admixture leads to art increased zero-field splitting and a large g-tensor anisotropy as manifested by the excited Rh(III) corroles.
机译：两个以Rh（III）为核心的5,10,15-三（五氟苯基）环（tpfc）的光激发态分别为Rh（pyr）（PPh3）（tpfc）和Rh（PPh3）（tpfc）通过时间分辨电子顺磁共振（TREPR）结合脉冲激光激发进行了研究。使用瞬态章动技术，将自旋极化光谱分配给光激发三重态。观察到的两种Rh（III）分子的光谱宽度主要取决于Rh（III）金属离子上的轴向配体。在Rh（PPh3）（tpfc）的情况下，发现TREPR光谱延伸超过200 mT，这比非过渡金属分子的光谱宽度大3倍以上。此外，Rh（ III）与非过渡金属腐蚀相比，它们的对称性差。可以根据与Rh（III）离子的过渡金属特征相关的强自旋轨道耦合（SOC）来合理化Rh（III）分子的TREPR光谱中的特性。假定光激发的Rh（III）分子中的SOC有效地将以金属为中心的（3）dd状态与以TREPR实验检测到的以金属为中心的（3）pi pi *状态混合。这种掺混导致艺术上增加的零场分裂和大的g张量各向异性，这由激发的Rh（III）腐蚀所证明。

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