1. Charge Delocalization of 1,4-Benzenedicyclometalated Ruthenium: A Comparison between Tris-bidentate and Bis-tridentate Complexes.
- Author
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Long-Zhen Sui, Wen-Wen Yang, Chang-Jiang Yao, Hai-Yan Xie, and Yu-Wu Zhong
- Subjects
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RUTHENIUM , *ELECTROCHEMICAL analysis , *ELECTRIC properties of metals , *OXIDATION , *ELECTRON paramagnetic resonance , *BIPYRIDINE - Abstract
A dimetallic biscyclometalated ruthenium complex, [(bpy)2Ru(dpb)Ru(bpy)2]2+ (bpy = 2,2'-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-phenyl-Ru) structural component with a previously reported bis-tridentate complex, [(tpy)Ru(tpb)Ru(tpy)]2+ (tpy = 2,2';6',2?-terpyridine; tpb = 1,2,4,5-tetra-2-pyridylbenzene). The charge delocalizations of these complexes across the Ru-phenyl-Ru 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. [ABSTRACT FROM AUTHOR]
- Published
- 2012
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