Dinuclear Ru-Cu Complexes: Electronic Characterisation and Application to Dye-Sensitised Solar Cells
Dinuclear Ru-Cu Complexes: Electronic Characterisation and Application to Dye-Sensitised Solar Cells
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双核钌-铜配合物：电子表征及其在染料敏化太阳能电池中的应用
DOI：
10.1002/ejic.201001039
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发表时间：
2010
影响因子：
2.3
通讯作者：
McCall K
中科院分区：
文献类型：
--
作者：
McCall K
我们制备了配合物[Ru {4,4 -(CO2R-bpy) 2}{Cu-(exoO2-cyclam)}][NO3] 2 [R= Et (1)， H(2)]，该配合物具有一个CuII中心共价连接（联吡啶基）RuII片段。通过循环伏安法、紫外/可见光谱、杂化DFT和TD-DFT（时间依赖密度泛函理论）计算、电子顺磁共振、发射光谱和紫外/可见光谱电化学对配合物进行了表征，后者显示出可逆转化为一氧化和二氧化以及一氧化和二还原物质。数据表明，第一次氧化主要基于Ru中心，但基于Ru和基于Cu的最高已占据轨道之间的能量差异很小。还发现了溶剂共溶的证据
We prepared the complexes [Ru {4, 4-(CO2R-bpy) 2}{Cu-(exoO2-cyclam)}][NO3] 2 [R= Et (1), H (2)], which possess a CuII centre covalently linked to a (bipyridyl) RuII fragment. The complexes were characterised by cyclic voltammetry, UV/Vis spectroscopy, hybrid DFT and TD-DFT (time-dependent density-functional theory) calculations, EPR (electron paramagnetic resonance), emission spectroscopy and UV/Vis spectroelectrochemistry, with the latter showing reversible conversion to the mono-and di-oxidised and monoand di-reduced species. The data suggest the first oxidation to be largely based on the Ru centre but with little energetic difference between the highest occupied orbitals based on Ru and based on Cu. There was also evidence of solvent co-