Theoretical model for the luminescing excited states of Ru (bpy)/sub 3//sup 2 +/ and Os(bpy)/sub 3//sup 2 +/ (bpy = 2,2'-bipyridine)
A theroetical model is developed here for the Metal to Ligand Charge Transfer (MLCT) excited states of Ru(bpy)/sub 3//sup 2 +/ and Os(bpy)/sub 3//sup 2 +/ assuming that the promoted electron is localized upon one bipyridine. The effects of ligand field splittings, spin-spin coupling, and spin-orbit coupling are included in the model. It is found that four low-lying excited-state behavior below 300K. A similar previously developed model that assumed that the promoted electron is delocalized over all three bipyridines is found to predict five low-lying states. The luminescence polarization and relative radiative and non-radiative decay lifetimes of the low-lying states for both models are predicted on the basis of the symmetry and the amount of singlet character in these states. It is found that the localized model can easily account for the available experimental data and that explicit states assignments can be made. Further, it is found that the delocalized model cannot radionalize the experimental data. It is concluded that the excited states must be viewed as localized in agreement with other experimental evidence. 6 figures, 6 tables.
- Research Organization:
- North Carolina Univ., Chapel Hill (USA). Dept. of Chemistry
- DOE Contract Number:
- AS05-78ER06034
- OSTI ID:
- 5992425
- Report Number(s):
- DOE/ER/06034-T7; ON: DE83014996
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
400201* -- Chemical & Physicochemical Properties
400301 -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
AZINES
BIPYRIDINES
COMPLEXES
ENERGY LEVELS
EXCITED STATES
HETEROCYCLIC COMPOUNDS
LIGANDS
LUMINESCENCE
MATHEMATICAL MODELS
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
OSMIUM COMPLEXES
PYRIDINES
RUTHENIUM COMPLEXES
TRANSITION ELEMENT COMPLEXES