Substitutent effects and bonding characteristics in (o-benzoquinone diimine)bis(bipyridine)ruthenium(II) complexes
Journal Article
·
· Inorganic Chemistry; (United States)
- York Univ., North York, Ontario (Canada)
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.
- OSTI ID:
- 7069055
- Journal Information:
- Inorganic Chemistry; (United States), Journal Name: Inorganic Chemistry; (United States) Vol. 32:3; ISSN 0020-1669; ISSN INOCAJ
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400500* -- Photochemistry
ABSORPTION SPECTROSCOPY
AMIDES
AMINES
AROMATICS
AZINES
BIPYRIDINES
CALCULATION METHODS
CHEMISTRY
COMPLEXES
ELECTROCHEMISTRY
ELECTRONIC STRUCTURE
ENERGY LEVELS
EXCITED STATES
HETEROCYCLIC COMPOUNDS
IMINES
LASER SPECTROSCOPY
MATHEMATICAL MODELS
MOLECULAR ORBITAL METHOD
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
PYRIDINES
QUINONES
RAMAN SPECTROSCOPY
RUTHENIUM COMPLEXES
SPECTROSCOPY
TRANSITION ELEMENT COMPLEXES
VOLTAMETRY
400500* -- Photochemistry
ABSORPTION SPECTROSCOPY
AMIDES
AMINES
AROMATICS
AZINES
BIPYRIDINES
CALCULATION METHODS
CHEMISTRY
COMPLEXES
ELECTROCHEMISTRY
ELECTRONIC STRUCTURE
ENERGY LEVELS
EXCITED STATES
HETEROCYCLIC COMPOUNDS
IMINES
LASER SPECTROSCOPY
MATHEMATICAL MODELS
MOLECULAR ORBITAL METHOD
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
PYRIDINES
QUINONES
RAMAN SPECTROSCOPY
RUTHENIUM COMPLEXES
SPECTROSCOPY
TRANSITION ELEMENT COMPLEXES
VOLTAMETRY