Synthesis of polyamines with pendant cyanoimidazole units and their electrochemical properties

✍ Scribed by Taeseok Jang; Paul G. Rasmussen

• Publisher: John Wiley and Sons
• Year: 1998
• Tongue: English
• Weight: 209 KB
• Volume: 36
• Category: Article
• ISSN: 0887-624X
• DOI: 10.1002/(sici)1099-0518(199810)36:14<2619::aid-pola22>3.0.co;2-k

✦ Synopsis

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 Ϫ2.6 to Ϫ2.7 V vs. Ag/Ag ϩ 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.