Supramolecular encapsulation of redox-active monomers to enable free-radical polymerisation.

Extended polymeric structures based on redox-active species are of great interest in emerging technologies related to energy conversion and storage. However, redox-active monomers tend to inhibit radical polymerisation processes and hence, increase polydispersity and reduce the average molecular weight of the resultant polymers. Here, we demonstrate that styrenic viologens, which do not undergo radical polymerisation effectively on their own, can be readily copolymerised in the presence of cucurbit[ n ]uril (CB[ n ]) macrocycles. The presented strategy relies on pre-encapsulation of the viologen monomers within the molecular cavities of the CB[ n ] macrocycle. Upon polymerisation, the molecular weight of the resultant polymer was found to be an order of magnitude higher and the polydispersity reduced 5-fold. The mechanism responsible for this enhancement was unveiled through comprehensive spectroscopic and electrochemical studies. A combination of solubilisation/stabilisation of reduced viologen species as well as protection of the parent viologens against reduction gives rise to the higher molar masses and reduced polydispersities. The presented study highlights the potential of CB[ n ]-based host-guest chemistry to control both the redox behavior of monomers as well as the kinetics of their radical polymerisation, which will open up new opportunities across myriad fields.