Issue 30, 2022

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

Abstract

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.

Graphical abstract: Supramolecular encapsulation of redox-active monomers to enable free-radical polymerisation

Supplementary files

Article information

Article type
Edge Article
Submitted
11 apr 2022
Accepted
06 iyn 2022
First published
07 iyn 2022
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2022,13, 8791-8796

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

S. Mommer, K. Sokołowski, M. Olesińska, Z. Huang and O. A. Scherman, Chem. Sci., 2022, 13, 8791 DOI: 10.1039/D2SC02072F

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements