Iron complexes as potential photocatalysts for controlled radical photopolymerizations: A tool for modifications and patterning of surfaces

ABSTRACT This article reports on the presumably first use of iron complexes (FeC) as potential photocatalysts for controlled radical photopolymerization reactions (CRP2). Three compounds were designed and investigated. Good linear evolutions of the molecular weight (Mn) with the conversion were observed. A comparison was provided with a reference iridium (III) complex Ir(ppy)3 where ppy stands for 2‐phenylpyridine. The on/off photopolymerization experiments highlight the presence of dormant species and a re‐initiation on demand upon irradiation. This unique re‐initiation property was used for the modification of surfaces (hydrophilic/hydrophobic properties) and surface patterning as well as the synthesis of a block co‐polymer (PMMA‐b‐PBA). A comparative analysis of the behavior of these iron complexes in thermally and photochemically activated polymerization was provided. The chemical mechanisms were studied by steady state photolysis, laser flash photolysis, cyclic voltammetry, luminescence quenching, and electron spin resonance experiments. A catalytic cycle was proposed with two steps: (i) the oxidation of the FeC excited state by an alkyl halide and (ii) the reduction by the oxidized form (FeC°+) by an amine or the macroradicals leading to the regeneration of the catalyst. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54 , 702–713