Poly-1,2-azepines by the photopolymerization of phenyl azides. Precursors for conducting polymer films

Polymers with a 1,2-azepinediyl structure are the primary products in the photopolymn. of aryl azides in a N atm. The polymers are through to be formed via singlet phenylnitrene and azacycloheptatetraene. The structure elucidation of these polymers is based on both spectroscopy and chem. anal. using a series of seven (substituted) Ph azides. The initially formed poly-1,2-azepines are very susceptible to oxidn.; delocalized charge species are formed upon exposure to air, while upon oxidative doping with I2 or AsF5 the polymers become elec. conductive. Conductivities ?10-2 S/cm are found. When the photopolymn. of aryl azides is performed in air, a simultaneous photooxidn. of the poly-1,2-azepines is obsd., furnishing carbonyl contg. polymers. Thin polymer films of poly-1,2-azepines are deposited on a fused silica window when the photopolymn. is carried out with gaseous PhN3. High-resoln. patterns of poly-1,2-azepines are formed when a photomask is used in this gas-phase polymn. Upon doping these patterns become elec. conductive. [on SciFinder (R)]