Polymers are ubiquitous in our everyday lives largely due to their low cost, processibility and broad range of mechanical properties. As technology advances researchers aim to develop new multi-functional polymers with unique mechanical, electrical, and optical properties such as shape-shifting soft robots and high-strength high-toughness films for aerospace applications. However, traditional isotropic polymers, with random polymer chain conformations, are not effective for many of these next-generation materials. There is increased interest in developing anisotropic polymers where researchers can precisely tune both the chemical makeup and physical alignment of polymer chains to obtain desired functionality. In this thesis, I develop two distinct intrinsically anisotropic polymers - liquid crystal elastomers (LCEs) and covalent organic frameworks (COFs) - which exhibit unique physical properties.

LCEs are soft materials that directly couple the anisotropy of liquid crystals to a loosely crosslinked polymer network. When exposed to a stimulus, such as heat, a reversible phase transition occurs which alters the optical and mechanical properties of the material and is promising in applications ranging from high damping materials to soft-robotics. Here, I develop a new method to program reversible complex actuations into shape shifting LCEs including a self-curling flower and a film that morphs in the topographical features of a human face. Next, I translate the synthesis procedure to a new reactive 3D printing method to enable more sophisticated shape changes. Finally, I can readily tune the actuation temperature of these LCEs so that they can actuate from body heat which is useful for biomedical applications.

COFs are highly porous and crystalline polymers with tunable pore sizes and functionality with applications in catalysis, filtration, energy storage, and high-strength films. However, COFs are traditionally very difficult to process and current methods to obtain free-standing films are not scalable and yield modest crystallinities. Here, I obtain high surface area and crystalline free-standing films directly from monomers. This procedure is quick and inexpensive compared to previous methods and is industrially scalable. Therefore, this is an important advancement in COF processing that has the potential to greatly expand research focused on the application of these multifunctional materials.