Structural and Dynamical Properties of n-Alkane Molecules in Clathrate Phase of Syndiotactic Polystyrene

Syndiotactic polystyrene (sPS) forms a clathrate phase with a variety of compounds. Not only rigid molecules but also flexible molecules can be stored in the cavities of the clathrate phase. To clarify the adjustment mechanism of a flexible guest molecule to the sPS clathrate system, the host and guest structures were investigated by means of solid-state ¹³C NMR and Raman spectroscopy, and X-ray diffractometry for the sPS clathrates with a series of n-alkanes from n-hexane to n-decane. Although the 010 spacing of the host sPS lattice expanded slightly on going from n-hexane to n-heptane, it decreased markedly at n-octane and then increased gradually with the chain length of guest n-alkane. The conformational change of guest n-alkane molecules was involved in this anomalous change in the 010 spacing. Majority of the n-hexane and n-heptane molecules took extended chain structures in the clathrates, whereas all longer n-alkanes took bent chain structures. The mean-square displacement of hydrogen atoms in the clathrates was estimated by quasielastic neutron scattering experiments. It was confirmed that the host lattice contraction suppressed thermal motion of the clathrate system.