Electrosynthesis and co-ordination chemistry of polymer films coated on electrode surfaces from pyrrole polypyridyls

New functionalized polypyrrole films containing transition-metal complexes of the type [Mn(bipy)(3)](2+) (bipy = 2,2'-bipyridine) and [M(I)L(diene)](+) (M = Rh or Ir, L = 2,2'-bipyridine or 1,10-phenanthroline, diene = cycloocta-1,5-diene or norborna-2,5-diene) have been synthesized and characterized by electrochemical techniques and UV/VIS spectroscopy. The strategy is based on the complexation of Mn2+ cations and [{(M(I)(diene)Cl}(2)] precursor complexes in polymer films, coated on platinum and carbon electrodes by oxidative electropolymerization of pyrrole-substituted 2,2'-bipyridine and 1,10-phenanthroline monomers in acidic MeCN electrolyte. The redox behaviour of poly[M(I)L(diene)(+)] is strongly dependent on the size of the cation of the supporting electrolyte. This appears to be a consequence of its permeation through the him to maintain electroneutrality in the polymer.