Abstract
Free radical polymerization (FRP) initiation from metal acetylacetonate–bidentate ligand interaction (MABLI) under mild conditions (room temperature, under air) is discussed here for different metal centers (Mn, V, and Cu). First, without light, in MABLI systems such as V(acac)3/2-diphenylphosphinobenzoic acid (2dppba), Mn(acac)3/2dppba, or Cu(acac)2/2dppba, electron-rich aryl (Ar•) radicals were conveniently and efficiently produced by the reaction of electron-poor acac• radicals with the iodonium salt (Iod), leading to an enhancement of pure redox (no light) polymerizations. Second, it was found that V(III)*/Iod reaction is generating aryl (Ar•) radicals at a high enough rate to initiate a photopolymerization process upon mild irradiation (LED@405 nm). This reaction can be implemented in redox photoactivated systems (e.g., using three-component V(acac)3/2dppba/Iod systems) in order to spectacularly enhance a slow redox process from 40 °C exothermicity in 800 s to 93 °C in less than 200 s. Third, an impr...
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