A NEW APPROACH TO THE STUDY OF OXIDATIVE POLYMERIZATION OF ANILINE AND TRANSFORMATIONS OF POLYANILINE - SUPPORT BY MEANS OF THE HUECKEL METHOD

An interrelationship between the mechanism of aniline polymerization a nd the direction of redox processes with participation of polyaniline chains on the one hand, and the pi-electron energy of oligoanilines wi th various numbers of units, degrees of oxidation and protonation on t he other hand, has been found for the first time. Calculations perform ed using the Hueckel method revealed that the difference in the pi-ele ctron energy of the oxidized and reduced forms of the chain correlated very well with the experimentally determined electrochemical potentia l for the respective redox transition. It is suggested that the Huecke l method can be used for investigation of the electrochemical activity of conjugated polymers obtained by oxidative polymerization, as well as for studying the mechanism of the latter. Copyright (C) 1996 Elsevi er Science Ltd.