Electronic Structural Studies of the Ru 3 (III,II,II) Mixed-Valent State of Oxo-Centered Triruthenium Clusters
Electronic Structural Studies of the Ru 3 (III,II,II) Mixed-Valent State of Oxo-Centered Triruthenium Clusters
复制标题
氧中心三钌团簇Ru 3 (III,II,II)混合价态的电子结构研究
DOI：
10.1021/acs.inorgchem.0c00881
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发表时间：
2020
影响因子：
4.6
通讯作者：
Kubiak, Clifford P.
中科院分区：
文献类型：
--
作者：
Palasz, Joseph M.;Porter, Tyler M.;Kubiak, Clifford P.
[Ru3O(OAc)6](CO)(L1)(L2)（L = 4-氰基吡啶、吡啶和N,N-二甲基氨基吡啶）类型的碱性乙酸钌配合物的阴离子态在近红外区域具有明显的光学跃迁，表明强耦合混合价态。制备了一系列这些簇，并结合密度泛函理论（DFT）计算结果进行了光谱研究，以构建轨道结构-函数描述，描述电子密度如何在这种混合价态的钌中心之间共享。混合价表现为等效钌中心的非键合原子轨道的组合，轨道之间的能量分裂增加，其对称性适合更有效的电子通信。这种基于 DFT 的模型与 Marcus-Hush 对混合价态的描述一致，并补充了特定轨道对两个氧化还原中心之间的电子耦合有不同程度贡献的知识。
The anionic state of basic ruthenium acetate complexes of the type [Ru3O(OAc)6](CO)(L1)(L2) (L = 4-cyanopyridine, pyridine, andN,N-dimethylaminopyridine) feature pronounced optical transitions in the near-infrared region indicative of strongly coupled mixed-valence states. A series of these clusters was prepared and studied spectroscopically in tandem with density functional theory (DFT) computational results to construct an orbital structure–function description of how the electron density is shared between the ruthenium centers in this mixed-valent state. The mixed-valency manifests itself as a combination of the nonbonding atomic orbitals of the equivalent ruthenium centers, with increased energetic splitting between the orbitals with symmetries appropriate for more efficient electronic communication. This DFT-based model agrees with the Marcus–Hush description of mixed-valency, with the added knowledge that specific orbitals contribute to different degrees in the electronic coupling between two redox centers.