NEW ELECTRICALLY CONDUCTIVE POLYMERS. DOPANT AND ARCHITECTURAL EFFECTS ON THE COLLECTIVE PROPERTIES OF COFACIALLY JOINED METALLOPHTHALOCYANINES.

An integrated chemical and physicochemical investigation of the cofacially joined metallomacrocyclic polymers left bracket M(PcO right bracket //n (M equals Si, Ge, Si) and the halogen-doped, electrically conductive derivatives left brace left bracket M(Pc)O right bracket X//y right brace //n (X equals I; M equals Si, Ge; X equals Br; M equals Si) is reported. The structures of these polymers have been studied by X-ray diffraction, resonance Raman, transmission infrared, transmission optical, **1**3C CP-MAS NMR, and EPR spectroscopy. The picture which emerges is that of inhomogeneously doped, mixed-valent arrays of predominantly ligand-oxidized ( pi radical cation) metallomacrocycles. Magnetic susceptibility and optical reflectivity measurements reveal a progressive increase in tight-binding bandwidths with decreasing interplanar (ring-ring) spacing. Studies of dc electrical conductivity as a function of dopant level and temperature suggest that transport in these heterogeneously doped materials can be satisfactorily described with percolation theory and fluctuation-induced carrier tunneling.