Silyloxyamines as Sources of Silyl Radicals: ESR Spin Trapping, Laser Flash Photolysis Investigation and Photopolymerization Ability

David-Louis Versace (1, 2) , Mohamad Ali Tehfe (1, 2) , Jacques Lalevée (1, 2) , Virginie Casarotto (1, 3) , Nicolas Blanchard (1, 3) , Fabrice Morlet-Savary (1, 2) , Jean-Pierre Fouassier (1, 2)

1 Université de Haute-Alsace (UHA) - Université de Haute-Alsace (UHA) Mulhouse - Colmar
2 DPG - Département de Photochimie Générale
3 COB - Laboratoire de Chimie organique et bioorganique

Two original silyloxyamines derived from 8-(pentamethyldisilyloxy)-julolidine and diethyl 3-(pentamethyldisilyloxy)-aniline are proposed as new sources of silyl radicals. The decomposition mechanism, the excited state processes and the radical generation are explored by steady state photolysis, laser flash photolysis, ESR and MO calculations. The Si-Si bond cleavage is clearly demonstrated. The formation of a radical cation on the amine moiety is also observed. Moreover, these compounds work as efficient Type I and Type II photoinitiators of free radical photopolymerization.

Mots clés: Physical Sciences

Domaines: Polymères

David-Louis Versace, Mohamad Ali Tehfe, Jacques Lalevée, Virginie Casarotto, Nicolas Blanchard, et al.. Silyloxyamines as Sources of Silyl Radicals: ESR Spin Trapping, Laser Flash Photolysis Investigation and Photopolymerization Ability. Journal of Physical Organic Chemistry, 2010, 24 (4), pp.342. ⟨10.1002/poc.1762⟩. ⟨hal-00599801⟩