POSS-Containing Jacketed Polymer: Hybrid Inclusion Complex with Hierarchically Ordered Structures at Sub-10 nm and Angstrom Length Scales

A series of organic-inorganic hybrid polymers, PnPOSS (n = 6, 10, which is the number of carbon atoms in the flexible alkyl spacers), containing a mesogen-jacketed liquid crystalline polymer (MJLCP) as the main chain and a crystalline nanobuilding block, polyhedral oligomeric silsesquioxane (POSS), in the side chains were designed and synthesized for constructing a hybrid inclusion complex. The phase structures and phase transitions of PnPOSS were investigated by differential scanning calorimetry, polarized light microscopy, wide-angle X-ray diffraction, small-angle X-ray scattering, and high-resolution transmission electron microscopy. With the competitive self-assemblies of the two covalently connected building blocks, namely MJLCP and POSS moieties, PnPOSS shows various phase structures including a sub-10 nm hexagonal columnar (Col(h)) or columnar nematic liquid crystalline phase, an angstrom rhombohedral crystalline (KR) phase, and a hierarchically ordered phase with Col(h) and K-R coexisting. This work provides a new approach for the design and synthesis of hybrid inclusion materials.