Electrochemistry and spectroscopy of ortho-metalated complexes of Ir(III) and Rh(III)
The electrochemical and UV-visible spectroscopic properties of Rh(III) and Ir(III) complexes of the ortho-metalating (NC) ligands, 2-phenylpyridine (ppy) and benzo(h)quinone (bzq), have been studied. Cyclic voltammetric studies of several of the dimeric species, (M(NC)/sub 2/Cl)/sub 2/, indicate metal-centered oxidation occurs at moderate potentials. Cationic monomers of the type M(NC)/sub 2/(NN)/sup +/ where (NN) = 2,2'-bipyridine or 1,10-phenanthroline have been prepared by reaction of the chelating ligands with the parent dimers. Cyclic voltammetric studies of these monomers indicate that several reversible ligand-centered reductions are generally observed and that the chelating ligand is more easily reduced than is the ortho-metalating ligand. Spectroscopic studies of the mixed ligand monomers indicate that dual emissions from MLCT states associated with the ortho-metalating and chelating ligands occur in the Ir(III) complexes whereas a single emission from a ligand-localized excited state is observed in the Rh(III) complexes. These results are discussed in terms of electronic and nuclear coupling factors analogous to those encountered in descriptions of bimolecular energy and electron-transfer processes.
- Research Organization:
- North Carolina State Univ., Raleigh
- OSTI ID:
- 7042280
- Journal Information:
- J. Phys. Chem.; (United States), Vol. 91:5
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
BENZOQUINONES
ELECTROCHEMISTRY
REDUCTION
IRIDIUM COMPLEXES
PYRIDINES
RHODIUM COMPLEXES
DIMERS
EXPERIMENTAL DATA
LIGANDS
ULTRAVIOLET SPECTRA
VISIBLE SPECTRA
VOLTAMETRY
AROMATICS
AZINES
CHEMICAL REACTIONS
CHEMISTRY
COMPLEXES
DATA
HETEROCYCLIC COMPOUNDS
INFORMATION
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
QUINONES
SPECTRA
TRANSITION ELEMENT COMPLEXES
400400* - Electrochemistry