Controlling the direction of the molecular axis of rod-shaped binuclear ruthenium complexes on single-walled carbon nanotubes
Controlling the direction of the molecular axis of rod-shaped binuclear ruthenium complexes on single-walled carbon nanotubes
复制标题
单壁碳纳米管上棒状双核钌配合物分子轴方向的控制
DOI：
10.1002/chem.201504678
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发表时间：
2016
期刊：
影响因子：
--
通讯作者：
Masa-aki Haga
中科院分区：
文献类型：
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作者：
iroaki Ozawa;Kazuma Kosaka;Tomomi Kita;Kai Yoshikawa;Masa-aki Haga
我们报道了混合价钌络合物的合成，该络合物在配体的一侧带有芘部分作为锚定基团。由混合价钌配合物和单壁碳纳米管组成的复合材料是通过单壁碳纳米管表面和钌配合物的芘锚之间的非共价π-π相互作用制备的。在这些复合材料中，Ru 配合物的长轴平行于 SWNT 的主方向排列。通过分子力学计算了这些复合物在单壁碳纳米管表面的优化构象。通过 UV/Vis 吸收、FT-IR 光谱、XPS 和 SEM 分析对复合材料进行了检查。此外，还评估了它们的电化学性能。复合材料的循环伏安图显示出相对于 Fc+/Fc 的峰值氧化电位 (Epox) = 0.86 和 1.08 V 处的可逆氧化波，分别归属于双核钌配合物的 RuII-RuII/RuII-RuIII 和 RuII-RuIII/RuIII-RuIII 氧化事件。基于这些观察，我们得出结论，双核钌配合物的电化学性质和混合价态在附着到单壁碳纳米管表面后得以保留。
We report the synthesis of a mixed‐valence ruthenium complex, bearing pyrene moieties on one side of the ligands as anchor groups. Composites consisting of mixed‐valence ruthenium complexes and SWNTs were prepared by noncovalent π–π interactions between the SWNT surface and the pyrene anchors of the Ru complex. In these composites, the long axis of the Ru complexes was aligned in parallel to the principal direction of the SWNT. The optimized conformation of these complexes on the SWNT surface was calculated by molecular mechanics. The composites were examined by UV/Vis absorption and FT‐IR spectroscopy, XPS, and SEM analysis. Furthermore, their electrochemical properties were evaluated. Cyclic voltammograms of the composites showed reversible oxidation waves at peak oxidation potentials (Epox) = 0.86 and 1.08 V versus Fc+/Fc, which were assigned to the RuII‐RuII/RuII‐RuIIIand the RuII‐RuIII/RuIII‐RuIIIoxidation events of the dinuclear ruthenium complex, respectively. Based on these observations, we concluded that the electrochemical properties and mixed‐valence state of the dinuclear ruthenium complexes were preserved upon attachment to the SWNT surface.