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.
|Title of host publication||Journal of Polymer Science, Polymer Symposia|
|Editors||Christopher W. Allen|
|Number of pages||29|
|Publication status||Published - 1983|
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