Laser flash photolysis study of electron transfer reactions of phenolate ions with aromatic carbonyl triplets
Light-induced electron transfer reactions from phenolate ions to a variety of carbonyl triplets have been studied in aqueous acetonitrile by using 337.1-nm laser flash photolysis. In particular, the effects of carbonyl triplet nature and substitution in phenolate ions have been examined with respect to both kinetics and primary photoproduct yields. The rate constants for electron transfer are found to be in the range 2 x 10/sup 9/-1 x 10/sup 10/ M/sup -1/ s/sup -1/. The quantum yields of primary photoproducts (phenoxy radicals and radical anions of carbonyl compounds) are essentially unity except with p-bromo- and p-iodophenolate ions. With p-iodophenolate ion, the yields of ketone-derived radical ions are in the range 0.3 to 0.5 and remain practially unchanged on increasing the temperature from 23 to 75/sup 0/C. This result suggests the involvement of heavy atom induced intersystem crossing and/or back electron transfer at some stage(s) of the electron transfer reaction mechanism. 6 figures, 4 tables.
- Research Organization:
- Univ. of Notre Dame, IN
- OSTI ID:
- 6447007
- Journal Information:
- J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 85:10; ISSN JPCHA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
400104 -- Spectral Procedures-- (-1987)
400301 -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
400500* -- Photochemistry
ACETONITRILE
ALKALI METAL COMPOUNDS
AQUEOUS SOLUTIONS
AROMATICS
BENZOPHENONE
CHEMICAL REACTION KINETICS
CHEMICAL REACTION YIELD
CRESOLS
DATA
DECAY
DISPERSIONS
ELECTROMAGNETIC RADIATION
ELECTRON TRANSFER
ENERGY-LEVEL TRANSITIONS
EXCITATION
EXPERIMENTAL DATA
HYDROGEN COMPOUNDS
HYDROXIDES
HYDROXY COMPOUNDS
INFORMATION
IONIZATION
KETONES
KINETICS
LASER RADIATION
MEDIUM TEMPERATURE
MIXTURES
MULTIPLETS
NITRILES
NUMERICAL DATA
ORGANIC BROMINE COMPOUNDS
ORGANIC CHLORINE COMPOUNDS
ORGANIC COMPOUNDS
ORGANIC FLUORINE COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
ORGANIC IODINE COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
OXYGEN COMPOUNDS
PHENOLATES
PHENOLS
PHOTOIONIZATION
RADIATIONS
RADICALS
REACTION KINETICS
SODIUM COMPOUNDS
SODIUM HYDROXIDES
SOLUTIONS
TEMPERATURE DEPENDENCE
TRIPLETS
YIELDS