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
