Symmetry breaking via polymer chain overcrowding in molecular bottlebrush crystallization*

One of the fundamental laws in crystallization is translational symmetry, which accounts for the profound shapes observed in natural mineral crystals and snowflakes. Spherical polymer crystalsomes have been grown and investigated in the context of spherical crystallography, where translational symmetry is broken be confining crystal growth in a curved liquid/liquid interface. In this talk, we present the spontaneous formation of spherical hollow crystals with broken translational symmetry in crystalline molecular bottlebrush (mBB) polymers. The unique structure was named as mBB crystalsome (mBBC), highlighting its similarity to the classical molecular vesicles. Fluorescence resonance energy transfer (FRET) experiments showed that the mBBC formation was driven by local chain overcrowding-induced asymmetrical lamella bending.