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- Title
Electronic Coupling between Two Amine Redox Sites through the 5,5′-Positions of Metal-Chelating 2,2′-Bipyridines.
- Authors
Nie, Hai-Jing; Chen, Xialing; Yao, Chang-Jiang; Zhong, Yu-Wu; Hutchison, Geoffrey R.; Yao, Jiannian
- Abstract
Electron delocalization of new mixed-valent (MV) systems with the aid of lateral metal chelation is reported. 2,2′-Bipyridine (bpy) derivatives with one or two appended di- p-anisylamino groups on the 5,5′-positions and a coordinated [Ru(bpy)2] (bpy=2,2′-bipyridine), [Re(CO)3Cl], or [Ir(ppy)2] (ppy=2-phenylpyridine) component were prepared. The single-crystal molecular structure of the bis-amine ligand without metal chelation is presented. The electronic properties of these complexes were studied and compared by electrochemical and spectroscopic techniques and DFT/TDDFT calculations. Compounds with two di- p-anisylamino groups were oxidized by a chemical or electrochemical method and monitored by near-infrared (NIR) absorption spectral changes. Marcus-Hush analysis of the resulting intervalence charge-transfer transitions indicated that electron coupling of these mixed-valent systems is enhanced by metal chelation and that the iridium complex has the largest coupling. TDDFT calculations were employed to interpret the NIR transitions of these MV systems.
- Publication
Chemistry - A European Journal, 2012, Vol 18, Issue 45, p14497
- ISSN
0947-6539
- Publication type
Article
- DOI
10.1002/chem.201201813