Mesomorphic behavior of polydiethylphosphazenes as described by¹³C,¹⁴N, and²H NMR

Abstract

The existence of mesomorphism in polydiethylphosphazene was recently established by MAS NMR and X-ray diffraction characterization. In the present work the mechanism of motion of the ethyl side groups in the high-temperature polymorph tabove 45 C) is identified and compared to the arrangement of side groups in the low-temperature polymorph. For this purpose a few NMR active nuclei (¹³C,¹⁴N, and²H) were exploited to define the side-chain motions occurring at transition. Experiments performed at varying temperatures close to the onset of solid transition suggest the presence of jumps between two conformations in the pretransition state. Rotor-synchronized triple-resonance NMR of the high-temperature phase determined the average distances between the carbons and the nitrogens in the polymorphs. The theoretical prediction of the dipolar interaction between the nuclei supports the hypothesis that ethyl groups can undergo a complete rotation about the P CH₂ bond by jumping across a conformational barrier. The mechanism of motion of the ethyl groups must be cooperative and the collapse of the rigid shell around the main chain is described at the transition.