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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Vibronic Participation of the Bridging Ligand in Electron Transfer and Delocalization: New Application of a Three-State Model in Pyrazine-Bridged Mixed-Valence Complexes of Trinuclear Ruthenium Clusters
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Vibronic Participation of the Bridging Ligand in Electron Transfer and Delocalization: New Application of a Three-State Model in Pyrazine-Bridged Mixed-Valence Complexes of Trinuclear Ruthenium Clusters

机译：配体在电子转移和离域中的振动参与：三态模型在三核钌簇的吡嗪桥联混合价络合物中的新应用

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摘要

The importance of the bridging ligand in mediating electronic communication and delocalization between charge centers in near-delocalized mixed-valence complexes is investigated in the specific context of pyrazine-bridged, hexanuclear ruthenium complexes that display electron-transfer rates on the order of 10~(11)-10~(12)s~(-2), as observed by partial coalescence of infrared bands. It is shown that a three-state vibronic model explicitly including the electronic and vibrational participation of the bridging ligand is needed to account for infrared and resonance Raman evidence of vibronic activity in symmetric modes of the bridging pyrazine ligand. The specific molecular orbital and normal-mode basis for this application of the three-state model is presented using experimental observations and density functional calculations on model trinuclear ruthenium clusters. An important conclusion of the application of this model is that infrared activity of symmetric bridging ligand modes in mixed-valence complexes is not a reliable indicator of electronic asymmetry on the vibrational time scale. The three-state model is shown to qualitatively reproduce the "tunability" of electronic communication observed in these complexes. The central importance of such a direct consideration of the bridging ligand in similar near-delocalized or delocalized complexes (like the well-known Creutz-Taube ion) is re-emphasized in this study.
机译：在吡嗪桥联，六核钌络合物显示电子传递速率约为10〜（ 11）-10〜（12）s〜（-2），通过红外波段的部分合并观察到。表明，需要三态振动学模型，明确包括桥接配体的电子和振动参与，以解决桥连吡嗪配体在对称模式下振动活性的红外和共振拉曼证据。使用模型三核钌簇的实验观察和密度泛函计算，为三态模型的这种应用提供了特定的分子轨道和正态基础。该模型应用的重要结论是，混合价络合物中对称桥联配体模式的红外活性不是振动时标上电子不对称性的可靠指标。三态模型显示出定性地再现了在这些复合物中观察到的电子通信的“可调性”。在这项研究中再次强调了直接考虑桥接配体在类似的近离域或离域复合物中（如众所周知的Creutz-Taube离子）的中心重要性。

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