Silyloxyamines as sources of silyl radicals: ESR spin‐trapping, laser flash photolysis investigation, and photopolymerization ability

Two silyloxyamines derived from 8‐(pentamethyldisilyloxy)‐julolidine and diethyl 3‐(pentamethyldisilyloxy)‐aniline are proposed as new sources of silyl radicals. The decomposition mechanism, excited state processes and the radical generation are explored by steady state photolysis, laser flash photolysis (LFP), electron spin resonance (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 (PI) of free radical photopolymerization (FRP).