Synthesis of poly(phenylgermanosilanes) and poly(phenylgermanocarbosilanes)

Abstract

Phenyl-substituted poly(germanosilanes) and poly(germanocarbosilanes) have been synthesized through the Wurtz-Kipping reaction via dechlorination of mixtures of dichlorophenylsilanes (PhSi(R)Cl2, where R = H, Ph, or vinyl) with diphenyldichlorogermane in the presence of an ultradisperse sodium suspension. The polymers thus synthesized have been investigated by X-ray fluorescence analysis; FTIR and UV spectroscopy; and 1H, 13C, and 29Si NMR spectroscopy. The peak maxima in the UV spectra of the polymers dissolved in THF are in the wavelength range of 300–375 nm. Under the effect of UV irradiation with a wavelength of 320–380 nm, photoluminescence emission peaking in the range of 380–470 nm is observed. Size exclusion chromatography indicates that all the (co)polymers under examination are characterized by a narrow GPC curve and their polydispersity indexes are no larger than 1.5. According to dynamic TGA data, the weight loss of the polymers reaches 80% even at 500°C. Owing to formation of branched structures in vinyl-substituted copolymers, the GPC curves widen (the polydispersity index is ∼6), while the yield of an inorganic residue at 900°C amounts to 40%.