Preparation and reactivity of metal-containing monomers

Abstract

Earlier we described the synthesis, properties 2 and regularities of radical polymerization 3 of some first-row transition-metal methacryloylacetonates and reported the characreristics of the polymers produced. It has been noted that Fe III and CuII methacryloylacetonates practically do not polymerize under the conditions studied. This fact is assumed 4 to be due to the intramolecular termination of the chain resulting from the transfer of an electron from the growing macroradical to the metal ion. EXAFS data support this suggestion, confirming partial reduction of the metal ion during the polymerization of Cun methacryloylacetonate. 5 The termination of the polymer chain can be avoided by reducing the metal ions in the monomeric complexes beforehand or by constantly regenerating the active radical centers. Both of these conditions are feasible during the electrochemical polymerization of metallomonomers. The advantages of this method are that it is possible to strictly control for chain initiation and termination, and to produce electrodes modified by metallopolymers and possessing electrocatalytic activity. In the present work we studied the redox properties and the possibility of electropolymerization of CulI and Fe III methacryloylacetonates and methacryloylacetone designated hereinafter as (MAA)2Cu, (MAA)3Fe, and (MAA), respectively.