Stereoregular High-Density Bottlebrush Polymer and Its Organic Nanocrystal Stereocomplex through Triple-Helix Formation

We report the synthesis of a well-defined molecular bottlebrush polymer with stereoregular side chains (i.e., syndiotactic PMMA). The simultaneous control over the molecular weight, side-chain tacticity, and architecture allows the macromolecule to stereocomplex with the complementary linear stereoregular polymers (i.e., isotactic PMMAs) in controlled manners. By modulating the feed ratio of the complexing materials and chain length of the linear assembling component, a variety of crystalline materials with different sizes and morphologies, including discrete spherical nanoparticle, multiple-particle assembly, and cross-linked network structure, can be produced. Among these, uniformed sized, stable nanocrystals that exhibit temperature-induced solution assembly and disassembly properties can be derived from a combined process of PMMA triple-helix stereocomplex formation and polymer architecture-directed intramolecular crystallization. This work has established a new, facile synthetic protocol toward stimuli-responsive organic nanocrystals, which is applicable to the fabrication of a wide variety of functional crystal nanomaterials with practical applications