Beijing National Laboratory for Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China.
Inorg Chem. 2013 Apr 1;52(7):4040-5. doi: 10.1021/ic400082z. Epub 2013 Mar 18.
A multicenter redox-active system with a linear N-Ru-Ru-N array, where two distal triarylamine sites are bridged by a cyclometalated bisruthenium segment, has been synthesized and characterized with single-crystal X-ray analysis. This system displays four consecutive and separate anodic redox waves at low potentials, indicating the presence of amine-amine electronic coupling with a distance of 19.16 Å through the cyclometalated bisruthenium segment. In contrast, when a noncyclometalated bisruthenium bridge is used, no amine-amine coupling is present. Upon stepwise oxidation by chemical or electrochemical methods, four-step absorption spectral changes occur in the visible to near-infrared region. In addition, the EPR studies and DFT and TDDFT calculations of the singly oxidized state are presented.
一种具有线性 N-Ru-Ru-N 阵列的多中心氧化还原活性体系，其中两个远端三芳胺位点通过环金属化双钌片段桥接，已经通过单晶 X 射线分析进行了合成和表征。该体系在低电位下显示出四个连续且独立的阳极氧化还原波，表明通过环金属化双钌片段存在胺-胺电子耦合，其距离为 19.16 Å。相比之下，当使用非环金属化双钌桥时，不存在胺-胺偶联。通过化学或电化学方法逐步氧化，在可见近红外区域发生四步吸收光谱变化。此外，还呈现了单氧化态的 EPR 研究以及 DFT 和 TDDFT 计算。
