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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Structural, electrochemical and photophysical properties of an exocyclic di-ruthenium complex and its application as a photosensitizer
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Structural, electrochemical and photophysical properties of an exocyclic di-ruthenium complex and its application as a photosensitizer

机译：环外二钌配合物的结构，电化学和光物理性质及其在光敏剂中的应用

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摘要

The reaction of cis-bis(2,2'-bipyridine)dichlororuthenium(II) hydrate with a conformationally mobile bipyridyl macrocycle afforded [(bpy)(2)Ru(mu-L)Ru(bpy)(2)]Cl-4 center dot 6H(2)O, a bridged di-Ru complex. Single crystal X-ray diffraction showed the macrocyclic ligand adopting a bowl-like structure with the exo-coordinated Ru(II) centers separated by 7.29 angstrom. Photophysical characterization showed that the complex absorbs in the visible region (lambda(max) = 451 nm) with an emission maximum at 610 nm (tau = 706 ns, Phi(PL) = 0.021). Electrochemical studies indicate the di-Ru complex undergoes three one -electron reversible reductions and a reversible one-electron oxidation process. This electrochemical reversibility is a key characteristic for its use as an electron transfer agents. The complex was evaluated as a photocatalyst for the electronically mismatched Diets-Alder reaction of isoprene and trans-anethote using visible light. It afforded the expected product in good conversion (69%) and selectivity (dr > 10 :1) at low loadings (0.5-5.0 mol%) and the sensitizer/catalyst was readily recycled. These results suggest that the bipyridyl macrocycle could be widely applied as a bridging ligand for the generation of chromophore-catalyst assemblies.
机译：顺式-双（2,2'-联吡啶）二氯钌（II）水合物与构象可移动的联吡啶大环反应生成[（bpy）（2）Ru（mu-L）Ru（bpy）（2）] Cl-4中心点6H（2）O，桥连的二钌络合物。单晶X射线衍射显示大环配体采用碗状结构，其外配位的Ru（II）中心相隔7.29埃。光物理特征表明，该络合物在可见光区域吸收（λ（最大值）= 451 nm），最大发射波长为610 nm（tau = 706 ns，Phi（PL）= 0.021）。电化学研究表明二钌配合物经历了三个单电子可逆还原和一个可逆的单电子氧化过程。这种电化学可逆性是用作电子转移剂的关键特征。使用可见光，将该配合物评估为异戊二烯和反式蒽的电子失配的Diets-Alder反应的光催化剂。它在低负荷（0.5-5.0mol％）下提供了具有良好转化率（69％）和选择性（dr＞ 10∶1）的期望产物，并且敏化剂/催化剂易于再循环。这些结果表明联吡啶大环化合物可以广泛地用作生色团-催化剂组装体的桥联配体。

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