SYNTHESIS OF POLYAMINES WITH PENDANT CYANOIMIDAZOLE UNITS AND THEIR ELECTROCHEMICAL PROPERTIES

The 2-(1-methyl-4,5-dicyanoimidazolyl) group was attached to poly(dial lylamine) and polyethylenimine, affording polymers containing an elect ron-withdrawing pendant group. The key to their preparation is high re activity of 1-methyl-2-fluoro-4,5-dicyanoimidazole (1) toward nucleoph ilic aromatic substitution (NAS) reactions with aliphatic amines. Cycl ic voltammograms of these polymers show reduction waves at -2.6 to -2. 7 V vs. Ag/Ag+ but no reoxidation waves, unlike those of monomeric and oligomeric model compounds, which are quasi-reversible. The cyclic vo ltammetry studies of oligomeric model compounds with different alkyl s pacers show that the degree of quasi-reversibility decreases as dicyan oimidazoles are crowded together in a molecule, suggesting that a cert ain degree of chemical reaction occurs between reduced dicyanoimidazol e groups. (C) 1998 John Wiley & Sons, Inc.