Heterosubstituted Polysilanes

The reaction of phenylalkylpolysilanes (PhRSi) n (R = Me, Pr, Hex, Oct) with acetyl chloride/aluminum chloride or acetyl bromide/aluminum bromide yielded the new halogen-substituted polysilanes SiX 2 R−(SiXR) n −SiX 2 R (X = Cl, Br). These were further converted into alkoxy- or thioalkyl-substituted polysilanes, providing the first method for synthesizing such polymers. The halogenated polysilanes were also hydrogenated with LiAlH 4 to form hydropolysilanes SiH 2 R−(SiHR) n −SiH 2 R. All polysilanes were characterized by 1 H, 13 C, 29 Si NMR, GPC, and UV. The phenylalkylpolysilanes and p -methoxyphenylhexylpolysilane showed strong fluorescence in the near-UV.