Cooperative heterometallic catalysts: balancing activity and control in PCL- block -PLA copolymer synthesis.

Heterometallic cooperativity is gaining momentum in cyclic ester ring-opening polymerisation, yet remains surprisingly underexplored in their block copolymerisations. Here, we report the first homogeneous heterometallic "ate" catalysts for poly(ε-caprolactone)-poly(lactic acid) block copolymers, showcasing the substantial differences in the polymer structures observed upon exchanging Zn for Mg or Ca.