On the chain length effect: Comparative reactivity of a macroradical and a radical

The reactivity of two aminoalkyl radicals formed from ethyldimethylaminobenzoate (EDB) and a polymeric derivative (PoEDB) toward different additives such as oxygen, TEMPO, methylacrylate MA, phenols, an onium salt, CBr4 is investigated through Laser Flash Photolysis. The transient absorption spectra of the radicals are in a good agreement with the spectra calculated by using molecular orbitals calculations. The interaction rate constants with the different additives are measured. The reactivity of EDB and PoEDB radicals appears as quite similar. Quantum mechanical calculations support the experimental results.