ESR AND MAGNETIC-PROPERTIES OF ELECTRICALLY CONDUCTING METALLOPHTHALOCYANINE POLYMERS

Polymeric metallophthalocyanines of Cu, Ni, Co in which benzene rings are shared in common with the macrocyclic phthalocyanine rings contain ing peripheral carboxylic groups have been synthesized and their elect rical conductivities are shown to increase from 5 to 8 orders of magni tude by thermal treatment. The cobalt polymer exhibits greater conduct ivity than its nickel or copper analogs. The heated polymers show very broad electron spin resonance (ESR) signals and large paramagnetic su sceptibilities. The bulk magnetic susceptibility of these polymers sho ws Curie-like behavior when the samples are heated from room temperatu re to 473 K. This is explained on the basis of coexistence of fixed mo bile and conduction electron spins in the system and the interaction o f the soliton type defects present in these polymers with the polymeri c network to give dipolar charge carriers. This is also supported by t he decrease in ESR intensity with increasing temperature when the samp les are heated in the ESR cavity. The effect of the presence of unpair ed electrons on the d shell of the central metal atoms on the line wid th and the line shape of the ESR spectra is also explained. (C) 1994 J ohn Wiley & Sons, Inc.