Joint theoretical experimental investigation of the electron spin resonance spectra of nitroxyl radicals: Application to intermediates in in situ nitroxide mediated polymerization (in situ NMP) of vinyl monomers

Natalia Zarycz, Edith Botek, Benoît Champagne, Valérie Sciannaméa, Christine Jérôme, Christophe Detrembleur

Research output: Contribution to journalArticle


Density functional theory (DFT) calculations have been performed to address the structure of nitroxide intermediates in controlled radical polymerization. In a preliminary step, the reliability of different theoretical methods has been substantiated by comparing calculated hyperfine coupling constants (HFCCs) to experimental data for a set of linear and cyclic alkylnitroxyl radicals. Considering this tested approach, the nature of different nitroxides has been predicted or confirmed for (a) the reaction of C-pnenyl-N-tert-butylnitrone and AIBN, (b) N-tert-butyl-α-isopropylnitrone and benzoyl peroxide, (c) tert-butyl methacrylate polymerization in the presence of sodium nitrite as mediator, and (d) for the reaction of a nitroso compound with AIBN. Values of HFCC experimentally determined have been confirmed by DFT calculations.

Original languageEnglish
Pages (from-to)10432-10442
Number of pages11
JournalJournal of physical chemistry B
Issue number34
Publication statusPublished - 28 Aug 2008


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