Aminoalkyl Radicals: Direct Observation and Reactivity toward

Jul 3, 2007 - A large range of values are obtained: (0.04−3) × 109 M-1 s-1 for O2, .... ACS Macro Letters 2012 1 (1), 92-95 ... Macromolecules 0 (p...
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J. Phys. Chem. A 2007, 111, 6991-6998

6991

Aminoalkyl Radicals: Direct Observation and Reactivity toward Oxygen, 2,2,6,6-Tetramethylpiperidine-N-oxyl, and Methyl Acrylate J. Laleve´ e,* B. Graff, X. Allonas, and J. P. Fouassier Department of Photochemistry, UMR 7525 CNRS, UniVersity of Haute Alsace, ENSCMu, 3 rue Alfred Werner, 68093 Mulhouse Cedex, France ReceiVed: March 2, 2007; In Final Form: May 25, 2007

The reactivity of 11 aminoalkyl radicals toward different additives [oxygen, 2,2,6,6-tetramethylpiperidineN-oxyl (TEMPO), and methyl acrylate (MA)] has been investigated through laser flash photolysis and quantum mechanical calculations. The transient absorption spectra of the radicals were recorded: good agreement was found with the spectra calculated by using quantum mechanical calculations. All the interaction rate constants were measured. A large range of values are obtained: (0.04-3) × 109 M-1 s-1 for O2, (0.002-5) × 108 M-1 s-1 for TEMPO, and (