An insight into the redox activity of Ru and Os complexes of the N,N '-bis(2-pyridyl)benzene-1,2-diamine ligand: Structural, electrochemical and electronic structure analysis by density functional theory calculations

摘要

The synthesis of Ru and Os complexes of the ligand, N,N'-bis(2-pyridyl)benzene-1,2-diamine namely, [Ru-III(acac)(2)(Py-bqdi)], (9), (Ru-II(Ph-trpy)(Py-bqdi)Cl], (10) and (Os-II(bpy)(2)(Py-bqdi)](ClO4), ([11]ClO4) [where Py-bqdi = N,N'-dipyridyl-o-benzoquinonediimine, acac = 2,4-pentanedionate, Ph-trpy = 4'-phenyl-2,2':6',2 ''-terpyridine, bpy = 2,2'-bipyridine] is reported. The molecular structures of complexes 9-[11]ClO4 are authenticated by single crystal X-ray diffraction studies. The electronic structural properties of the complexes, in particular, the accessible oxidized/reduced forms of the complexes, are examined by using an array of analytical techniques (magnetic resonance, UV-Vis-NIR spectroscopy and electrochemistry). Comprehensive Density Functional Theory (DFT) calculations have also been carried out to provide additional support to the experimental work.