Recent advances in externally controlled ring-opening polymerisations

Switchable catalysis is a powerful tool in the polymer chemist's toolbox as it allows on demand access to a variety of polymer architectures. Switchable catalysts operate by the generation of a species which is chemically distinct in behaviour and structure to the precursor. This difference in catalytic activity has been exploited to allow spatiotemporal control over polymerisations in the synthesis of (co)polymers. Although switchable methodologies have been applied to other polymerisation mechanisms for quite some time, for ring opening polymerisation (ROP) reactions it is a relatively young area of research. Despite its infancy, the field is accelerating rapidly. Here, we review recent developments for selected external stimuli for ROP, including redox chemistry, light, allosteric and mechanical control. Furthermore, a brief review on switch catalysis involving exogeneous gases will also be provided, although this area differs from traditional switchable catalysis techniques. An outlook on the future of switchable catalysis is also provided.