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The structures of the "Z" and "R" substituents of a RAFT agent (Z-C(S)S-R) determine a RAFT agent's ability to control radical polymerization. In this paper we report new acid/base switchable N-aryl-N-pyridyl dithiocarbamates (R = -CH₂CN, Z = -N(Py)(Ar)) which vary in substituent at the 4-position of the aryl ring and the use of these to control molecular weight and dispersity. In their protonated form, the new RAFT agents are more effective in controlling polymerization of the more activated monomer, methyl acrylate (MA), whereas in their neutral form they provide more effective control of the polymerization of less activated monomers, N-vinyl carbazole (NVC) and vinyl acetate (VAc). For each polymerization, the apparent chain transfer coefficient (Ctrapp) shows a good correlation with Hammett parameters. Dithiocarbamates with more electron-withdrawing aryl ring substituents have the higher Ctrapp. This demonstrates the influence of polar effects on Ctrapp and supports the hypothesis that the activity of these RAFT agents is determined by the availability of the lone pair of the dithiocarbamate nitrogen. |
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