Substitutent effects and bonding characteristics in (o-benzoquinone diimine)bis(bipyridine)ruthenium(II) complexes

The effect of substitutents on the electrochemistry and electronic spectroscopy of Ru[sup II](bpy)[sub 2]LL complexes is reported, where bpy = 2,2[prime]-bipyridine and LL = 4,5-disubstituted o-benzoquinone diimines, o-semiquinone diimines, o-benzenediamides, and o-phenylenediamines. These data are...

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Veröffentlicht in:Inorganic chemistry 1993-02, Vol.32:3
Hauptverfasser: Masui, Hitoshi, Lever, A.B.P., Dodsworth, E.S.
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Sprache:eng
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Zusammenfassung:The effect of substitutents on the electrochemistry and electronic spectroscopy of Ru[sup II](bpy)[sub 2]LL complexes is reported, where bpy = 2,2[prime]-bipyridine and LL = 4,5-disubstituted o-benzoquinone diimines, o-semiquinone diimines, o-benzenediamides, and o-phenylenediamines. These data are used to create a map of the orbital energies as a function of the Hammett parameter of the substitutents, giving insight into the electronic behavior of these complexes. Electronic spectra are characterized with respect to energy, intensity, and bandwidth, and band are assigned with support from resonance Raman (rR) and FTIR data. The solvatochromism of the o-benzoquinone diimine species is discussed. The data are interpreted in the context of metal-ligand orbital mixing and electronic structure. An ab initio study of the uncomplexed ligand in its quinone diimine oxidation sate is also included. 63 refs., 10 figs., 4 tabs.
ISSN:0020-1669
1520-510X
DOI:10.1021/ic00055a005