Radical ions of poly(phenylsilyne) and poly(phenylgermyne)

Abstract

AbstractPoly(phenylsilyne) and poly(phenylgermyne), which have a network Si‐ and Ge‐skeleton, were synthesized by electrochemical reduction of trichlorophenylsilane and trichlorophenylgermane, respectively. The poly(phenylsilyne) showed broad absorption and emission bands that are characteristic of silicon network polymers. Similarly broad absorption and emission bands were observed for the poly(phenylgermyne). Radical anions and radical cations of poly(phenylsilyne) and poly(phenylgermyne) were produced by pulse radiolysis. The radical ions of these network polymers showed broad transient absorption bands from the UV to the IR region. Within 200 ns after pulse radiolysis, the absorption band of the radical cation in the UV region decreased, whereas the band in the IR region increased. The time‐dependent spectral change of the radical cation suggests the formation of a change resonance band of the delocalized positive charge on the σ‐conjugated polymer chain. In contrast to the radical cation, the radical anion of the network polymers did not show a spectral change.