Carbanion photochemistry. 8. Effect of substituent reduction potential on the ground- and excited-state isomerization of 2-aryl-1,3-diphenylpropenyl anions
Journal Article
·
· J. Org. Chem.; (United States)
The ground- and excited-state chemistry of 2-aryl-1,3-diphenylpropenyl anions is readily described by a Hueckel model. Because of the antisymmetric nonbonding molecular orbital, in the ground state none of the charge is distributed in the central ring. In the excited state, a nonbonding electron is promoted to a symmetric orbital which is localized on the central aryl ring. Thus lowering the reduction potential of the substituent stabilizes the excited state toward electro-transfer-initiated isomerization of cis-stilbene. Conversely, the more stabilized excited states undergo more efficient E,Z isomerization. Finally, if the central substituent is a 4-chlorophenyl group, photoinduced chloride elimination occurs. 17 references, 8 figures, 4 tables.
- Research Organization:
- Univ. of Kentucky, Lexington
- OSTI ID:
- 5186237
- Journal Information:
- J. Org. Chem.; (United States), Journal Name: J. Org. Chem.; (United States) Vol. 50:18; ISSN JOCEA
- 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
ANIONS
ARYL RADICALS
ATOMIC MODELS
CARBANIONS
CHARGE DISTRIBUTION
CHARGED PARTICLES
CHEMICAL REACTIONS
CHEMISTRY
DATA
ELECTRON TRANSFER
ENERGY LEVELS
ENERGY-LEVEL TRANSITIONS
EXCITATION
EXCITED STATES
EXPERIMENTAL DATA
GROUND STATES
INFORMATION
IONS
ISOMERIZATION
MATHEMATICAL MODELS
NUMERICAL DATA
PHOTOCHEMICAL REACTIONS
PHOTOCHEMISTRY
RADICALS
REDOX POTENTIAL
REDUCTION
400301 -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
400500* -- Photochemistry
ANIONS
ARYL RADICALS
ATOMIC MODELS
CARBANIONS
CHARGE DISTRIBUTION
CHARGED PARTICLES
CHEMICAL REACTIONS
CHEMISTRY
DATA
ELECTRON TRANSFER
ENERGY LEVELS
ENERGY-LEVEL TRANSITIONS
EXCITATION
EXCITED STATES
EXPERIMENTAL DATA
GROUND STATES
INFORMATION
IONS
ISOMERIZATION
MATHEMATICAL MODELS
NUMERICAL DATA
PHOTOCHEMICAL REACTIONS
PHOTOCHEMISTRY
RADICALS
REDOX POTENTIAL
REDUCTION