Key Laboratory of Pesticide and Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University, 152 Luoyu Road, Wuhan, Hubei 430079, China.
Chem Asian J. 2013 Sep;8(9):2023-32. doi: 10.1002/asia.201300419. Epub 2013 Jun 14.
A series of binuclear ruthenium-alkynyl complexes that are bridged by thiophene groups (thiophene, bithiophene, and terthiophene) have been synthesized. All of these complexes have been well-characterized by NMR spectroscopy, X-ray diffraction, and elemental analysis. The electronic properties of these complexes have been examined by using cyclic voltammetry, UV/Vis/NIR and IR spectroscopy, electron paramagnetic resonance (EPR) spectroscopy, and density functional theory (DFT) calculations. Electrochemical results showed that the potential difference (ΔE) and comproportionation constant (Kc) decreased with increasing size of the thiophene bridging unit. The UV/Vis/NIR spectra and TDDFT calculations of the monocations indicated that the NIR transitions displayed aromatic bridging character. EPR studies of the mono-oxidized radical species further demonstrated that the unpaired electron/hole was delocalized over both metals and the bridging ligand and established significant participation in the ligand oxidation.
已经合成了一系列由噻吩基团（噻吩、联噻吩和三噻吩）桥接的双核钌-炔基配合物。这些配合物都通过 NMR 光谱、X 射线衍射和元素分析得到了很好的表征。通过循环伏安法、紫外可见近红外和红外光谱、电子顺磁共振（EPR）光谱和密度泛函理论（DFT）计算研究了这些配合物的电子性质。电化学结果表明，随着噻吩桥接单元尺寸的增加，电位差（ΔE）和比例常数（Kc）减小。单阳离子的紫外可见近红外光谱和 TDDFT 计算表明，NIR 跃迁显示出芳香桥接特征。单氧化自由基物种的 EPR 研究进一步证明，未配对电子/空穴在两个金属和桥接配体上离域，并在配体氧化中发挥了重要作用。
