Syntheses of poly[(dimethyl)-co-(4,7,10,13-tetraoxatetradecylmethylsilanes)]. An evaluation of the use of C8K versus Na in the preparation of polysilanes

To evaluate the use of c8k versus na as the reducing agent in the preparation of polysilanes, the homopolymers poly(4,7,10,13-tetraoxatetradecylmethylsilanes) 1 and poly(dimethylsilane) 5 as well as the copolymers poly[(dimethyl)-co-(4,7,10,13-tetraoxatetradecylmethylsilanes)] 2–4 were synthesized from 4,7,10,13-tetraoxatetradecylmethyldichlorosilane (6) and/or dimethyldichlorosilane (7). C8k in comparison to na gave an increased yield and enhanced purity, when used with polar monomers, such as 6, that presumably intercalate into graphite. In the presence of increasing amounts of apolar 7 both a decrease in yield as well as purity is observed in the c8k based copolymerizations. In contrast, the type of monomer does not affect the results of the na based copolymerizations. Whereas at ambient temperatures the introduction of dimethylsilane units in 2–4, causes minor changes in the polysilane optical properties, as compared to 1, at low temperatures differences are discernible both in solution and the solid state (thin film) in the case of 4na. Apparently, the incorporated dimethylsilane moieties reduce the mean free energy of defect formation e, i. E. At these low temperatures the silicon backbone adopts a more extended conformation as reflected by the occurrence of an additional “abrupt” transition.