C\ idence of a one-electron transfer process in a carbene reaction has been observed for the first time. The exunple is the quench;ng of the photoescited triplet state of diphenylcarbene (3\*DPC) by electron donors. Measurement of the fluorescence lifetime as a function of donor concentration yielde
Picosecond laser studies of the effects of reactants on intramolecular energy relaxation of diphenylcarbene: Reaction of diphenylcarbene with alcohols
β Scribed by E.V. Sitzmann; J.G. Langan; K.B. Eisenthal
- Publisher
- Elsevier Science
- Year
- 1984
- Tongue
- English
- Weight
- 523 KB
- Volume
- 112
- Category
- Article
- ISSN
- 0009-2614
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β¦ Synopsis
Picosecond laser induced fluorescence measurements provide for the first time the direct meanrrement of the intramolccular and intermolecular energy decay dynamics of singlet diphenylcarbene (' DPC) in the presence of reactive molecules. As exemplified by the reaction of ' DPC with alcohols it is found that reactive molecules provide ' DPC witi not only a chemical decay channel but also an intramolecular decay channel which is due to a solvent polarity effect. These chemical and physical effects can act in opposite directions leading to novel results such as a sigtificaat increase in the sin$et state lifetime upon addition of reacting molecules. The absolute reaction rate constants of 'DPC with alcohols, in different solvents, obtained by direct measurements are also reported.
π SIMILAR VOLUMES
The singlet to triplet intersystem crossing rate (&) for a series of diphenylcarbene derivatives is found to be a sensitive function of the energy splitting (AEsT), which in turn depends on the solvent polarity and on the structure ofthe carbene. A turn-over in the dependence of ksr on AEsT is found
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