| Abstract
| - Treatment of poly(ferrocenylenemethylphenylsilylene) with iodine results in the formation of amorphous mixed-valence salts with localized electronic structure on the Mössbauer time scale. Variable-temperature spectroscopy indicates a reversible electron transfer with an activation energy of 4.7 kJ/mol. The transformations of [I3]-·nI2 clusters to I3- were proposed to accompany Fe(II)−Fe(III) oxidation.
- Structural and thermal characteristics of an amorphous iodine complex of a ferrocenylenesilylenepolymer, [−(C5H4)Fe(C5H4)Si(CH3)(C6H5)·(I1.5)−]n, have been measured using 57Fe Mössbauer, IR andRaman spectroscopy, X-ray diffraction, and thermomechanical analysis. The iodine-doped macromoleculesare mixed-valence salts with a localized electron structure on the 57Fe Mössbauer time scale, in whichferrocenylene units and ferrocenium moieties coexist. These macromolecules consist of blocks containingferrocenium moieties and sequences of nonoxidized ferrocenylene units. The environment about theferrocenium moieties consists of both single I3- and polyiodide [I3]-·nI2 species. Mössbauer data, collectedin the range 5−300 K, are interpreted in terms of the temperature dependence of the Lamb−Mössbauerfactor and reversible electron transfer with an activation energy of 4.7 kJ/mol. The transformations of[I3]- + I2 clusters to I3- are proposed to accompany Fe(II)−Fe(III) oxidation.
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