Near-edge x-ray absorption fine structure spectroscopy study of the photolytic process in poly(Phenyl thioether) with pendant iron moieties.

The near-edge x-ray absorption fine structure (NEXAFS) spectra of poly(Ph thioether) polymers with pendant Fe(Cp) iron moieties have been recorded at the carbon 1s, iron 2p, and phosphorus 1s and 2p edges. This study shows that soln. photofragmentation of the organometallic polymer causes the removal of iron moieties and the prepn. of the corresponding org. polymer: poly(Ph thioether). Spectroscopic characterization of poly(Ph thioether) prepd. in this manner indicates the presence of iron oxide, likely Fe2O3, and hexafluorophosphate counterion trapped in the demetalated polymer matrix. A photolytic examn. of the solid phase poly(Ph thioether)-Fe(Cp) organometallic polymer shows that irradn. of this polymer in air leads to the formation of poly(Ph thioether) and Fe2O3, while irradn. in vacuum leads to formation of iron species with a lower oxidn. state. The ability to probe the oxidn. state of this metal species is relevant to understanding how demetalation conditions affect the properties of the polymer.