A polysilane copolymer with reactive Si—H side groups was obtained through a homogeneous coupling reaction of dichlorodiphenylsilane with dichloromethylsilane. The reaction was carried out in a tetrahydrofuran (THF) solution of a sodium‐potassium alloy complex with 18‐crown‐6 with a well defined composition of alkali metal ion pairs (Mt+/crown ether, Mt–) at –75°C. The product was characterized using 1H NMR, 13C NMR, FT‐IR and UV/Visible spectroscopies and gel permeation chromatography. The results were compared with those obtained by the heterogeneous coupling reaction of the same monomers.
Summary: This work presents the first synthesis of a new polymer obtained by catalytic addition of the SiH groups of a poly[methyl(H)silane‐co‐methylphenylsilane] backbone to an N‐(allyl)cycloimmonium salt. This hybrid polymer was characterized by spectroscopic analysis, thermogravimetric analysis and gel‐permeation chromatography (GPC). The pendant N‐(allyl)cycloimmonium segments lead to the formation of molecular dipoles, as evidenced by electrical polarization experiments.Structure of the polysilane‐cycloimmonium salt.imageStructure of the polysilane‐cycloimmonium salt.
The toxicity of viologens can be significantly reduced by including them in tight [2]rotaxane structures alongside β-cyclodextrin, thus turning them into candidates of pharmaceutical interest. Here, we report a synthesis pathway for a benign viologen, by capping a small β-cyclodextrin-caged molecule, the 4,4'-bipyridine, with minimal-length presynthesized axle-stopper segments of the propyl-3-pentamethyldisiloxane type. After 90 min from the oral administration to laboratory mice, the product concentration in the bloodstream reaches a value equivalent to 0.634% of the initial dose of 800 mg·kg(-1). As compared to the nude viologen having the same structure, which proved to be lethal in doses of 40 mg·kg(-1), the product induces reversible morphological changes in the liver, kidney, lung, and cerebellum, up to a dose of 400 mg·kg(-1), with higher dosages giving rise to a chronic slow evolution.
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