Reversible metalation/demetalation of a polypyrrole matrix builds around catenand complexing cavities

Summary form only given. New functionalized polypyrrole films containing transition metal complexes have teen prepared and studied. The strategy is based on the three-dimensional template effect of a metal center (Cu/sup l/, Co/sup II/, Zn/sup II/, Ag/sup I/) able to entwine two end-functionalized chelating ligands before polymerization. The ligands used consist of a 2,9-diphenyl-1, 10-phenanthroline subunit (dpp) bearing two pyrrole nuclei. The rigidity of the polymer matrix is sufficient to allow demetalation of the template center (by CN/sup -/ or SCN/sup -/) without collapse of the three-dimensional structure. Such a property is related to the expected complex topology of the organic backbone which certainly contains interlocking rings and various network substructures. The free ligand polymer film can be recomplexed using an appropliate metal source. Low oxidation states like copper(I), cobalt(I), formal zinc(I) and silver(0) are remarkably stabilized by the entwined and entangled system. Conductivity measurements and detailed electrochemical and spectroelectrochimical studies on several films have been carried out.