Influence of Triplet Surface Properties on Excited-State Deactivation of Expanded Cage Bis(tridentate)Ruthenium(II) Complexes.
Influence of Triplet Surface Properties on Excited-State Deactivation of Expanded Cage Bis(tridentate)Ruthenium(II) Complexes.
复制标题
三重态表面性质对扩展笼双（三齿）钌（II）配合物激发态失活的影响。
DOI：
10.1021/acs.jpca.9b02927
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发表时间：
2019
期刊：
影响因子：
--
通讯作者：
P. Persson
中科院分区：
文献类型：
--
作者：
Lisa A. Fredin;P. Persson
激发态势能面（PES）的计算可用于预测与过渡金属配合物失活级联相关的关键特性。在这里，我们首先对相关激发态最小值进行完全自由优化，然后根据感兴趣的最小值进行广泛的二维 PES 计算。两个双齿 RuII 配合物 [Ru(DQP)2]2+ 和 [Ru(DQzP)2]2+ 的最低三重激发态表面图用于解释最近的实验结果，包括激发态寿命中意想不到的数量级差异。计算揭示了两种配合物最低三重激发态能量表面的基本形状和自旋跃迁的显着差异，特别是表明激发态寿命较短的[Ru(DQzP)2]2+的金属到配体电荷转移(MLCT)表面区域明显小于[Ru(DQP)2]2+。这导致在 [Ru(DQzP)2]2+ 的 MLCT 附近或 [Ru(DQP)2]2+ 的 MC 附近，三线态和单线态表面之间的能量交叉最小。这些结果表明，实验观察到的激发态寿命差异与能量可及的 3MLCT 构象密切相关。
Calculations of excited-state potential energy surfaces (PESs) are useful to predict key properties relating to the deactivation cascade of transition-metal complexes. Here, we first perform full free optimizations of the relevant excited-state minima, followed by extensive two-dimensional PES calculations based on the minima of interest. Maps of the lowest triplet excited-state surfaces of two bistridentate RuII-complexes, [Ru(DQP)2]2+ and [Ru(DQzP)2]2+, are used to explain recent experimental findings including an unexpected order of magnitude difference in an excited-state lifetime. The calculations reveal significant differences in the fundamental shapes and spin transitions of the lowest triplet excited-state energy surfaces of the two complexes and, in particular, show that the metal-to-ligand charge transfer (MLCT) surface region of [Ru(DQzP)2]2+ with a shorter excited-state lifetime is significantly smaller than that of [Ru(DQP)2]2+. This leads to a minimum energy crossing between the triplet and singlet surfaces near the MLCT for [Ru(DQzP)2]2+ or near the MC for [Ru(DQP)2]2+. These results indicate that the experimentally observed difference in the excited-state lifetime is closely related to the set of energetically accessible 3MLCT conformations.
影响因子：
3.3
作者：
Halcrow, Malcolm A.
通讯作者：
Halcrow, Malcolm A.
影响因子：
20.6
作者：
A. Vlček;A. Vlček;S. Záliš
通讯作者：
A. Vlček;A. Vlček;S. Záliš