On anomalies in the dependence of the electrical conductivity of polymeric ion-radical salts of 7,7,8,8-tetracyanoquinodimethane on aliphatic ionene polycation structure

Complex ion-radical salts of 7,7,8,8-tetracyanoquinodimethane (TCQM) containing polycations of symmetrical aliphatic ionenes have been synthesized, and their electrical conductivity investigated in relation to the concentration of the neutral TCQM and the method of preparation. In addition the temperature dependence of the electrical conductivity was investigated. High conductivity was observed for the complex salt of 6,6-ionene synthesized by a two-stage method (ϱ = 85ohm·cm for TCQM : TCQM∸ = 1·5). The anomalous high ϱ values of this salt (up to 107 ohm·cm) reported earlier are attributed to chemical and phase heterogeneity due to poor solubility of the simple salt of ionene-6,6, which has high crystallinity. An X-ray study of the complex salt shows that a new crystalline phase is formed when TCQM is added to the simple salt even up to TCQM/TCQM∸ = 1·5, above which level TCQM separates to form a new phase. Changes in the activation energy of conductivity and in the pre-exponent accompanying an increase in the TCQM concentration are satisfactorily accounted from a qualitative standpoint in the light of the present-day theory of conductivity of highly heterogeneous structures.