Radiative properties and charge-transfer character of the phosphorescent triplet state in mixed rhodium chelates
Journal Article
·
· Journal of Physical Chemistry; (United States)
- Univ. of Amsterdam (Netherlands)
The kinetics of the lowest excited [sup 3][pi]-[pi]* states of the complex cations [Rh(thpy)[sub 2](bpy)][sup +] and [Rh(thpy)(phpy)(bpy)][sup +] (thpy = 2,2[prime]-thienylpyridine, phpy = 2-phenylpyridine, bpy = bipyridine), co-doped in a single crystal of [Rh(phpy)[sub 2](bpy)]PF[sub 6], has been studied by means of optically detected microwave recovery and adiabatic rapid passage experiments. The population decay of the ligand-localized triplet-state sublevels in the complex cations is found to be 3 orders of magnitude faster than in the free ligand molecules. The decay of the [sup 3][pi]-[pi]* states of the complex cations is largely radiative in nature. The enhanced radiative decay is discussed to arise from selective spin-orbit coupling-induced mixing with [sup 1]d-[pi]* charge-transfer configurations. In these [sup 1]d-[pi]* configurations, metal ion d-orbitals forming a molecular orbital with ligand orbitals via [sigma]-bonding are of particular relevance for explaining the differences among the emissive properties of the triplet-state sublevels as determined experimentally. 39 refs., 4 figs., 4 tabs.
- OSTI ID:
- 5526381
- Journal Information:
- Journal of Physical Chemistry; (United States), Journal Name: Journal of Physical Chemistry; (United States) Vol. 97:39; ISSN JPCHAX; ISSN 0022-3654
- Country of Publication:
- United States
- Language:
- English
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· J. Phys. Chem.; (United States)
·
OSTI ID:7031796
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Related Subjects
14 SOLAR ENERGY
140505 -- Solar Energy Conversion-- Photochemical
Photobiological
& Thermochemical Conversion-- (1980-)
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
CALCULATION METHODS
CHARGE TRANSPORT
CHELATES
COMPLEXES
CONVERSION
CRYSTAL DOPING
DOPED MATERIALS
ENERGY CONVERSION
ENERGY LEVELS
EXCITED STATES
LIGANDS
LUMINESCENCE
MATERIALS
MICROWAVE SPECTRA
MOLECULAR ORBITAL METHOD
PHOSPHORESCENCE
RHODIUM COMPLEXES
SOLAR ENERGY CONVERSION
SPECTRA
TRANSITION ELEMENT COMPLEXES
140505 -- Solar Energy Conversion-- Photochemical
Photobiological
& Thermochemical Conversion-- (1980-)
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
CALCULATION METHODS
CHARGE TRANSPORT
CHELATES
COMPLEXES
CONVERSION
CRYSTAL DOPING
DOPED MATERIALS
ENERGY CONVERSION
ENERGY LEVELS
EXCITED STATES
LIGANDS
LUMINESCENCE
MATERIALS
MICROWAVE SPECTRA
MOLECULAR ORBITAL METHOD
PHOSPHORESCENCE
RHODIUM COMPLEXES
SOLAR ENERGY CONVERSION
SPECTRA
TRANSITION ELEMENT COMPLEXES