Abstract We describe the synthesis and characterization of triarylamine ethynyl ruthenium conjugate (4-OMeC6H4)2N-{C6H4-4-C≡C-RuCp* (dppe)}, 3. Its electronic and spectroscopy properties are investigated by anodic voltammetry, IR and UV–vis–NIR spectroelectrochemistry, and density functional theory (DFT) calculations. Results indicate that 3 undergoes two well-defined single-electron redox processes and that the RuII/III process occurs prior to the N0/+ process as supported by IR spectra ν(C≡C) band changes from 3 to 3+ (Δν = 129 cm−1) and spin-density distribution calculations of 3+. TDDFT calculations further reveal the NIR characteristic bands of singly oxidized 3+ from experimental spectroscopic absorptions, and we observe NAr2→Ru charge transfer mixed with Ru-C≡C→phenyl bridge charge-transfer.

中文翻译：

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钌乙炔基-三芳胺混合价共轭体系：合成、（光谱）电化学和理论计算

摘要 我们描述了三芳胺乙炔基钌共轭物 (4-OMeC6H4)2N-{C6H4-4-C≡C-RuCp* (dppe)}, 3 的合成和表征。通过阳极伏安法、IR 和UV-vis-NIR 光谱电化学和密度泛函理论 (DFT) 计算。结果表明 3 经历了两个明确定义的单电子氧化还原过程，并且 RuII/III 过程发生在 N0/+ 过程之前，IR 光谱 ν(C≡C) 带从 3 变为 3+ (Δν = 129 cm−1) 和 3+ 的自旋密度分布计算。TDDFT 计算进一步从实验光谱吸收揭示了单氧化 3+ 的 NIR 特征带，我们观察到 NAr2→Ru 电荷转移与 Ru-C≡C→苯桥电荷转移混合。