Synthesis and Coordination Chemistry of Poly(4-Vinyl-4'-methyl-2.2'-Bipyridine) Films on Electrode Surfaces

摘要

Two classes of synthetic precursors to polymeric films, zinc(vbpy)3(2+) and M(xbpy)(COD)+ (vbpy is 4-vinyl-4'methyl-2,2'-bipyridine; COD is 1,5-cyclooctadiene; M is Rhodium(I) or Iridium(I), have been prepared and found to undergo facile reductive electropolymerization on platinum, glassy carbon, or gold on polyester electrodes. The resulting films are themselves synthetic precursors to metal-free poly-(vbpy) films since the metals can be removed by complexation with sodium dibenzyldithiocarbamate or tertiary phosphines. The metal ions can be reincorporated into the film matrix by soaking in solutions containing appropriate salts or complexes. For example, poly-(Zn)vbpy)3)2+ undergoes facile metal exchange with CoCl2 in CH3CN(methyl cyanide) to give poly-(Co(vbpy)3)2+; a Co-containing film that can not be prepared by direct electropolymerization. Reprints.