The Role of Shape and Size of Guest Molecules in the Formation of Clathrates and Intercalates of Syndiotactic Polystyrene

The crystal structure of syndiotactic polystyrene (sPS) co-crystals of δ-class is discussed with the aim of identifying molecular descriptors that allow predicting the lattice distortions induced by the inclusion of guest molecules inside the cavities of the nanoporous δ-form. Based on the consideration that monoclinic and triclinic clathrates and intercalates of sPS form as a result of the unique deformability of the cavities of the δ-form, the identified parameters are the fractional occupancy factors of the undeformed cavity of the δ-form from guests along the a-axis, the c-axis, and the normal to the (010) planes of the crystals, and the relative orientation of the guests to the chain axes.