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Stereocomplexation is a useful strategy for the enhancement of polymer properties by the co-crystallization of polymer strands with opposed chirality. Yet, with the exception of PLA, stereocomplexes of biodegradable polyesters are relatively underexplored and the relationship between polymer microstructure and stereocomplexation remains to be delineated, especially for copolymers comprising two different chiral monomers. In this work, we resolved the two enantiomers of a non-symmetric chiral anhydride (CPCA) and prepared a series of polyesters from different combinations of racemic and enantiopure epoxides and anhydrides, via metal-catalyzed ring-opening copolymerization (ROCOP). Intriguingly, we found that only specific chiral combinations between the epoxide and anhydride building blocks result in the formation of semicrystalline polymers, with a single stereocenter inversion inducing a change from amorphous to semicrystalline copolymers. Stereocomplexes of the latter were prepared by mixing an equimolar amount of the two enantiomeric copolymers, yielding materials with increased melting temperatures (ca. 20 °C higher) compared to their enantiopure constituents. Following polymer structure optimization, the stereocomplex of one specific copolymer combination exhibits a particularly high melting temperature (Tm = 238 °C). 

Pentacoordinate Al catalysts comprising bipyridine (bpy) and phenanthroline (phen) backbones were synthesized and their catalytic activity in epoxide/anhydride copolymerization was investigated and compared to ( t-Bu salph)AlCl. Stoichiometric reactions of tricyclic anhydrides with Al alkoxide complexes produced ring-opened products that were characterized by NMR spectroscopy, mass spectrometry, and X-ray crystallography, revealing key regio- and stereochemical aspects.