Crystalline Hetero‐Stereocomplexed Polycarbonates Produced from Amorphous Opposite Enantiomers Having Different Chemical Structures

Stereocomplexation is the stereoselective interaction between two opposite enantiomeric polymers through an interlocked orderly assembly. Most studies focus on the stereocomplex formation from the crystalline opposite enantiomers having the identical structure; nevertheless, rare examples were reported regarding the crystalline stereocomplexes from enantiomeric polymers having different chemical structures. Herein we show a strategy for polymer orderly assembly through the formation of crystalline hetero‐stereocomplexed polymeric materials by the cocrystallization of amorphous isotactic polycarbonates with different chemical structures and opposite configurations. The behaviors in the crystalline state are significantly different from that of the component enantiomeric polymers or their homo‐stereocomplexes. This study is expected to open up a new way to prepare various semicrystalline materials having a wide variety of physical properties and degradability.