Br. Saunders et al., A PHYSICAL AND SPECTROSCOPIC STUDY OF POLYPYRROLE FILMS CONTAINING TETRASULFONATED METALLOPHTHALOCYANINE AND TRANSITION-METAL EDTA CHELATES, Synthetic metals, 69(1-3), 1995, pp. 363-364
The effect of the incorporated counteranion on the structure and prope
rties of polypyrrole is of fundamental interest. In the present study,
polypyrrole films containing tetrasulfonated metallophthalocyanine (M
PcTs, M = Co and Fe) and transition metal EDTA (MEDTA, M = Co, Cr, and
Fe) counteranions are examined by a variety of techniques including e
lemental analysis, conductivity, X-ray diffraction, SEM, TEM, EPR and
Mossbauer spectroscopy. The conductivity stability of PPyCrEDTA is sup
erior to that of both PPyMPcTs and the well known p-toluenesulfonate s
ystem (PPyPTS). TEM studies of PPyCoEDTA reveal some crystallinity. By
taking advantage of the presence of paramagnetic and Mossbauer active
metal ions, the environment of the counteranion within PPyMPcTs and P
PyMEDTA is examined by means of EPR and Mossbauer spectroscopy. The fo
rmer technique reveals a strong magnetic interaction between the unpai
red electrons of the polymer and the paramagnetic metal ion centres, a
nd the origin of this interaction is discussed. Structural models for
PPyMPcTs and PPyMEDTA are presented.