The structure of the organic intrinsically conducting polymers polypyrrole and poly(3-n.decylpyrrole) was investigated by x-ray diffraction. The liquid monomers pyrrole and 3-n.decylpyrrole were also measured. From the analysis of all the data, information on the molecular and intermolecular correlations in the polymers was obtained. Both the polymeric systems are found to maintain a substantial planarity of the aromatic rings, i.e., the alkylic substituent in poly(3-n.decylpyrrole) does not affect the planarity of the compound. Possible effects related to the size of the counterion are also discussed.

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Homo and copolymers of N-vinylpyrrole (NVP) were synthesized and the structure/properties relationships of the chemical oxidation products with FeC13 at different Fe3+/NVP molar ratios characterized. From DC electrical, FT-IR and Raman spectroscopic characterizations, the picture of a composite at a molecular level emerges as that of a block copolymer of non-conducting and conducting segments, these last derived from the oxidation of PNVP. The possibility of giving an estimate of the growth of the oxidation level is seen from FT-IR data, whereas Raman spectroscopy seems to be specifically sensible to the modifications induced by the oxidation in the NIR-Vis absorption, probably coupled to the enhancement of the conduction process. The transport properties are analyzed according to the hopping model and the result of fitting procedures discussed.