Conducting Polymers: Partially Oxidized Bridge-Stacked Metallophthalocyanines

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Abstract
The synthesis and characterization of a novel class of polymeric phthalocyanines (Pc), (PcMX)n (M-Al, Ga, Cr; X˭F and M-Si, Ge, Sn; X˭0) of exceptional thermal stability are summarized. These materials possess a linear MX backbone surrounded by a sheath of cofacial M-centered Pc rings. (PcAlF)n and (PcGaF)n are sublimable (10−3mmHg,540°C and 430°C, respectively) allowing for thin film formation. Iodine-doping leading to compositions (PcMXIy)n with y ranging from 0.06 to 5.5 is reported. Thermogravimetric analysis has proven useful for iodine analyses and has revealed that the order of thermal stability with regard to loss of iodine is (PcCrFIy)n < (PcGaFIy)n< (PcAlFIy)n < (PcSioIy)n. Raman spectra point to I3-and I5-as the principle polyiodide species, though their relative proportions vary depending on M and doping level. Increases in the electrical conductivity by as much as 109 with maximum conductivities in the range of 0.01–1 ohm−1cm−1 result from iodine doping. Conduction appears to be thermally activated (77–300K) with an apparent activation energy of 0.04eV. It is likely that electron transport is primarily ligand based and is metal-like in character.