Stereoengineering of poly(1,3-methylenecyclohexane) via two-state living coordination polymerization of 1,6-heptadiene.

External control over the rate of dynamic methyl group exchange between configurationally stable active species and configurationally unstable dormant species with respect to chain-growth propagation within a highly stereoselective and regiospecific living coordination polymerization of 1,6-heptadiene has been used to generate a spectrum of different physical forms of poly(1,3-methylenecyclohexane) (PMCH) in which the stereochemical microstructure has been systematically varied between two limiting forms. The application of this strategy to manipulate the bulk properties of PMCH and the solid-state microphase behavior of well-defined PMCH-b-poly(1-hexene) block copolymers is further demonstrated.