Charge Delocalization of 1,4-Benzenedicyclometalated Ruthenium: A Comparison between Tris-bidentate and Bis-tridentate Complexes

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• 作者：Long-Zhen Sui ; Wen-Wen Yang ; Chang-Jiang Yao ; Hai-Yan Xie ; Yu-Wu Zhong
• 刊名：Inorganic Chemistry
• 出版年：2012
• 出版时间：February 6, 2012
• 年：2012
• 卷：51
• 期：3
• 页码：1590-1598
• 全文大小：525K
• 年卷期：v.51,no.3(February 6, 2012)
• ISSN：1520-510X

文摘

A dimetallic biscyclometalated ruthenium complex, [(bpy)₂Ru(dpb)Ru(bpy)₂]²⁺ (bpy = 2,2鈥?bipyridine; dpb = 1,4-di-2-pyridylbenzene), with a tris-bidentate coordination mode has been prepared. The electronic properties of this complex were studied by electrochemical and spectroscopic analysis and DFT/TDDFT calculations on both rac and meso isomers. Complex [(bpy)₂Ru(dpb)Ru(bpy)₂]²⁺ has a similar 1,4-benzenedicyclometalated ruthenium (Ru鈥損henyl鈥揜u) structural component with a previously reported bis-tridentate complex, [(tpy)Ru(tpb)Ru(tpy)]²⁺ (tpy = 2,2鈥?6鈥?2鈥?terpyridine; tpb = 1,2,4,5-tetra-2-pyridylbenzene). The charge delocalizations of these complexes across the Ru鈥損henyl鈥揜u array were investigated and compared by studying the corresponding one-electron-oxidized species, generated by chemical oxidation or electrochemical electrolysis, with DFT/TDDFT calculations and spectroscopic and EPR analysis. These studies indicate that both [(bpy)₂Ru(dpb)Ru(bpy)₂]³⁺ and [(tpy)Ru(tpb)Ru(tpy)]³⁺ are fully delocalized systems. However, the coordination mode of the metal component plays an important role in influencing their electronic properties.