Polypyrrole (PPy) is of great potential importance due to its excellent conductive properties; however, a major obstacle to commercialization (like many synthetic metals) is its poor stability, especially to oxidation. Here is reported a new synthesis of PPy in the presence of the cobaltabisdicarbollide anion (see Figure), whose uniform distribution throughout the polymer leads to a dramatic improvement in the overoxidation threshold.

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Crystalline films on the surface of a polypyrrole (see Figure for SEM image) are obtained electrochemically from cobalt(bis‐dicarbolide)‐doped polypyrrole in aqueous Bu4N+Cl–, or (less effectively) in Bu4P+Cl– solution. The films, which are unidirectional (inwards) cation barriers, are highly stable in aqueous media, apparently due to the anion’s extremely low water solubility, but are easily dissolved in acetonitrile.

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