CIDNP studies of photoinitated electron-transfer reactions. Sensitized isomerization of an electron acceptor norbornadiene

Journal Article · Wed Oct 20 04:00:00 EDT 1982 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00385a022· OSTI ID:6199458

Schwarz, W ^[1]; Dangel, K M; Jones, G II; Bargon, J

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1. IBM Research Lab., San Jose, CA

Chemically induced dynamic nuclear polarization (CIDNP) has been observed on irradiation of dimethylbicyclolhepta-2,5-diene-2,3-dicarboxylate (3) in the presence of aromatic electron-donor sensitizers in acetonitrile. Nuclear polarization is detected for selected protons of 3 (emission) and its quadricyclene valence isomer 4 (enhanced absorption). The complementary CIDNP effects are rationalized in terms of the quenching of hydrocarbon singlets via electron transfer, intersystem crossing between resultant singlet and triplet radical-ion pairs, and competition between singlet and triplet ion recombination. The energetics of recombination allow that triplet level is above or below that of 3. The CIDNP effects are discussed in terms of other photochemical results regarding the electron-transfer photosensitized isomerization, 3 ..-->.. 4.

• OSTI ID: 6199458
• Journal Information: J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 104:21; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400301* -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
ALKENES
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
CYCLOALKENES
DIENES
ELECTRON TRANSFER
HYDROCARBONS
ISOMERIZATION
KINETICS
NMR SPECTRA
NORBORNADIENE
ORGANIC COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
POLYENES
REACTION KINETICS
SPECTRA