Radical ion/triplet mechanism for sensitized valence photoisomerization of a norbornadiene

Journal Article · Fri Jan 01 04:00:00 EST 1982 · J. Phys. Chem.; (United States)

DOI:https://doi.org/10.1021/j100210a008· OSTI ID:5422855

Jones, G II; Schwarz, W; Malba, V

Quenching of the fluorescence of a series of electron donor aromatic hydrocarbons in acetonitrile by dimethyl bicyclo(2.2.1)hepta-2,5-diene-2,3-dicarboxylate results in isomerization of the norbornadiene with varying efficiency. Quantum yield, CIDNP, and flash photolysis results are consistent with a rearrangement mechanism involving electron transfer from the sensitizer, intersystem crossing of resultant radical-ion pairs, and ion recombination to give norbornadiene triplets followed by rearrangement to the valence isomer. Where energetic factors are favorable, the isomerization quantum yield is as high as 0.39 and the efficiency of formation of norbornadiene triplets via ion recombination as high as 65%.

• Research Organization: Boston Univ., MA
• OSTI ID: 5422855
• Journal Information: J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 86:13; ISSN JPCHA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400301 -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
400500* -- Photochemistry
ANTHRACENE
AROMATICS
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
CONDENSED AROMATICS
DATA
DE-EXCITATION
DECOMPOSITION
ELECTRON TRANSFER
ENERGY LEVELS
ENERGY TRANSFER
ENERGY-LEVEL TRANSITIONS
EXPERIMENTAL DATA
FLUORESCENCE
HYDROCARBONS
INFORMATION
ISOMERIZATION
KINETICS
LUMINESCENCE
NMR SPECTRA
NUMERICAL DATA
ORGANIC COMPOUNDS
P STATES
PHENANTHRENE
PHOTOCHEMICAL REACTIONS
PHOTOLYSIS
PYRENE
RADIATIONLESS DECAY
RADICALS
REACTION KINETICS
S STATES
SPECTRA
STRUCTURAL CHEMICAL ANALYSIS
TRIPHENYLENE