Abstract
Poly(di-n-hexylsilylene) is composed of a crystalline phase (I) in which the silicon main chain has an all-trans or planar zigzag conformation, together with a less ordered phase (II) in which non-trans conformations are present. The solid state 29Si NMR spectrum exhibits two resonances, the more shielded of which corresponds to Phase II. A I → II transition occurs at 40°–42°C, above which only the more shielded 29Si resonance is observed. The 13C spectra are consistent with the disordering of the sidechains in Phase II. The Phase I 13C resonances exhibit a doubling which is not at present understood. Poly(di-n-pentylsilylene) and poly(di-n-butylsilylene) exhibit I → II transitions at 70° and 87°, respectively. Their 29Si spectra show strikingly different behavior from that of the poly(di-n-hexylsilylene). The crystalline phase (I) shows a more shielded resonance than that of the disordered phase. This is consistent with the X-ray findings of a 7/3 helical backbone bond arrangement. The Phase I 13C spectrum of poly(di-n-butylsilylene) shows peak doubling similar to that of the dihexyl polymer.
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Bovey, F.A., Schilling, F.C. (1991). The Solid State 29Si and 13C NMR of Poly(Di-n-Alkylsilylenes). In: Mathias, L.J. (eds) Solid State NMR of Polymers. Springer, Boston, MA. https://doi.org/10.1007/978-1-4899-2474-2_18
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DOI: https://doi.org/10.1007/978-1-4899-2474-2_18
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