ON POLYMERIZATION OF SOME HETEROCYCLIC 5-MEMBERED RING DONORS IN THE CHANNELS OF THE 3-DIMENSIONAL COORDINATION POLYMER [(ME3PB)3FE(CN)6]INFINITY

Various heterocyclic five-membered ring donors have been shown to be c ompletely or partially oxidized within the cavities of the three-dimen sional host polymer [(Me3Pb)3FeIII(CN)6]infinity to give polymeric int ercalated or charge transfer complexes respectively. The structure and physical properties of these complexes depend on the type of the hete rocyclic species, the time of the reaction, the exposure to light, atm ospheric oxygen or moisture and the degree of grinding. Pyrrole, N-met hylpyrrole, 2,5-dimethylpyrrole and pyrrolidine polymerize within the cavity of the host polymer to form the corresponding neutral semicondu cting diamagnetic polymeric intercalated complexes, the host network b eing fully reduced to its anionic homologue [(Me3Pb)3Fe(II)(CN)6-]infi nity. However, if the reaction mixture is treated with a few drops of water, there is a large increase in conductivity, and the complexes be come good semiconductors. In contrast, thiazole and thiophene do not p olymerize under these conditions, but give paramagnetic charge transfe r complexes.