Photosensitization of quadricyclene isomerization by electron acceptors. A short-circuit nonradiative decay mechanism for electron donor-acceptor quenching in polar media
Journal Article
·
· J. Phys. Chem.; (United States)
- Boston Univ., MA
Quantum efficiencies are reported for valence isomerization of quadricyclene to norbornadiene induced on quenching the excited singlet state of electron acceptor sensitizers. The notable feature is the large reduction in yield of isomerization in a polar solvent (acetonitrile) compared with reported data for similar photolysis in nonpolar media. A comparison of isomerization yields and flash photolysis results based on the mode of sensitization (i.e., singlet quenching vs. triplet quenching vs. excitation of ground-state charge-transfer complexes) leads to a distinction among exciplex, contact ion pair, and solvent-separated ion-pair intermediates which are potentially involved in electron donor-acceptor quenching.
- OSTI ID:
- 6497812
- Journal Information:
- J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 86:15; ISSN JPCHA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400301* -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
400500 -- Photochemistry
ACETONITRILE
ALKENES
AROMATICS
CHEMICAL REACTION YIELD
CHEMICAL REACTIONS
COMPARATIVE EVALUATIONS
CONDENSED AROMATICS
CYCLOALKENES
DATA
DECOMPOSITION
DISPERSIONS
EFFICIENCY
ELECTRON TRANSFER
EMISSION SPECTROSCOPY
ENERGY LEVELS
EXCITED STATES
EXPERIMENTAL DATA
FLUORESCENCE SPECTROSCOPY
HYDROCARBONS
INFORMATION
ION PAIRS
ISOMERIZATION
MIXTURES
NITRILES
NORBORNADIENE
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
ORGANIC SOLVENTS
PHOTOCHEMICAL REACTIONS
PHOTOLYSIS
QUADRICYCLENE
QUANTUM EFFICIENCY
REACTION INTERMEDIATES
REAGENTS
SENSITIZERS
SOLVENTS
SPECTROSCOPY
YIELDS
400301* -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
400500 -- Photochemistry
ACETONITRILE
ALKENES
AROMATICS
CHEMICAL REACTION YIELD
CHEMICAL REACTIONS
COMPARATIVE EVALUATIONS
CONDENSED AROMATICS
CYCLOALKENES
DATA
DECOMPOSITION
DISPERSIONS
EFFICIENCY
ELECTRON TRANSFER
EMISSION SPECTROSCOPY
ENERGY LEVELS
EXCITED STATES
EXPERIMENTAL DATA
FLUORESCENCE SPECTROSCOPY
HYDROCARBONS
INFORMATION
ION PAIRS
ISOMERIZATION
MIXTURES
NITRILES
NORBORNADIENE
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
ORGANIC SOLVENTS
PHOTOCHEMICAL REACTIONS
PHOTOLYSIS
QUADRICYCLENE
QUANTUM EFFICIENCY
REACTION INTERMEDIATES
REAGENTS
SENSITIZERS
SOLVENTS
SPECTROSCOPY
YIELDS