Ground- and excited-state electron-transfer reactions: photoinduced redox reactions of poly(pyridine)ruthenium(II) complexes and cobalt(III) cage compounds
Journal Article
·
· Inorg. Chem.; (United States)
Rate constants for the quenching of poly(pyridine)ruthenium(II) (RuL/sub 3//sup 2 +/) excited states by caged cobalt(III) amine complexes (Co(cage)/sup 3 +/) range from 2 x 10/sup 8/ to 1 x 10/sup 9/ M/sup -1/ s/sup -1/ at 25/sup 0/C. The quenching process involves parallel energy transfer (k/sub en/ approx. 1 x 10/sup 8/ M/sup -1/ s/sup -1/) and electron transfer (k/sub el/ = (0.1-1) x 10/sup 9/ M/sup -1/ s/sup -1/) from RuL/sub 3//sup 2 +/ to Co(cage)/sup 3 +/. The rate constants for electron-transfer quenching are consistent with expectations based on an adiabatic semiclassical model. The yields of electron-transfer products range from 0.3 to 1.0, increasing as the rate constants for the back-reaction of RuL/sub 3//sup 3 +/ with Co(cage)/sup 2 +/ diminish. The relatively low magnitudes of the back-reaction rate constants, (0.08-8) x 10/sup 8/ M/sup -1/ s/sup -1/, are consistent with the high yields of electron-transfer products and derive from poor coupling of the RuL/sub 3//sup 3 +/ and Co(cage)/sup 2 +/ orbitals. 30 references, 3 figures, 4 tables.
- Research Organization:
- Brookhaven National Lab., Upton, NY
- OSTI ID:
- 6507318
- Journal Information:
- Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 23:18; ISSN INOCA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400500* -- Photochemistry
AMINES
AZINES
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
COBALT COMPLEXES
COMPLEXES
CORRELATIONS
DATA
DATA ANALYSIS
DECOMPOSITION
ELECTRON TRANSFER
ENERGY LEVELS
EXCITED STATES
EXPERIMENTAL DATA
GROUND STATES
HETEROCYCLIC COMPOUNDS
INFORMATION
KINETICS
MATHEMATICAL MODELS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
PHOTOCHEMICAL REACTIONS
PHOTOLYSIS
PYRIDINES
REACTION KINETICS
REDOX REACTIONS
RUTHENIUM COMPLEXES
TRANSITION ELEMENT COMPLEXES
400500* -- Photochemistry
AMINES
AZINES
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
COBALT COMPLEXES
COMPLEXES
CORRELATIONS
DATA
DATA ANALYSIS
DECOMPOSITION
ELECTRON TRANSFER
ENERGY LEVELS
EXCITED STATES
EXPERIMENTAL DATA
GROUND STATES
HETEROCYCLIC COMPOUNDS
INFORMATION
KINETICS
MATHEMATICAL MODELS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
PHOTOCHEMICAL REACTIONS
PHOTOLYSIS
PYRIDINES
REACTION KINETICS
REDOX REACTIONS
RUTHENIUM COMPLEXES
TRANSITION ELEMENT COMPLEXES