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The 2‐(1‐methyl‐4,5‐dicyanoimidazolyl) group was attached to poly(diallylamine) and polyethylenimine, affording polymers containing an electron‐withdrawing pendant group. The key to their preparation is high reactivity of 1‐methyl‐2‐fluoro‐4,5‐dicyanoimidazole (1) toward nucleophilic aromatic substitution (NAS) reactions with aliphatic amines. Cyclic 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 voltammetry studies of oligomeric model compounds with different alkyl spacers show that the degree of quasi‐reversibility decreases as dicyanoimidazoles are crowded together in a molecule, suggesting that a certain degree of chemical reaction occurs between reduced dicyanoimidazole groups. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. A Polym. Chem. 36: 2619–2629, 1998

The electron accepting 1-methyl-4,5-dicyanoimidazole group was attached to vinyl polymers, via an alkoxy link, by nucleophilic aromatic substitution (NAS) of 1-methyl-2-fluoro-4,5-dicyanoimidazole (1) with poly(vinyl alcohol), or conventional polymerizations of vinyl monomers containing 1-methyl-2-oxo-4,5-dicyanoimidazole. The cyclic voltammetry (CV) studies show that monomeric and oligomeric model compounds are electrochemically quasi-reversible and the degree of reversibility decreases as dicyanoimidazoles become more proximate within a molecule. On the other hand, the polymers show much less reversible reduction waves at Ϫ2.6ϳϪ2.7 V vs Ag/Ag ϩ , suggesting that there are chemical reactions among the pendent groups reduced at relatively high potential.