Structure and properties of polyaniline as modeled by single-crystal oligomers

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Abstract
A single‐crystal charge–transfer complex of a phenyl‐end‐capped tetramer of polyaniline has been synthesized and studied along with a similar dimer of polyaniline. Structural, optical, and electrochemical studies of these oligomers in various oxidation states provide detailed information which has been used to model the structure of polyaniline and its evolution during electronic doping. These studies of the polymer and its oligomers suggest that the emeraldine salt form of the polymer (50% doping per nitrogen) is a preferred low‐energy structure. The preference for this structure leads to phase segregation in doped compositions having average doping levels less than 50%.