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

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cam.depositDate2022-06-06
cam.issuedOnline2022-06-07
dc.contributor.authorMommer, Stefan
dc.contributor.authorSokołowski, Kamil
dc.contributor.authorOlesińska, Magdalena
dc.contributor.authorHuang, Zehuan
dc.contributor.authorScherman, Oren A
dc.contributor.orcidMommer, Stefan [0000-0003-1400-5681]
dc.contributor.orcidSokołowski, Kamil [0000-0002-2481-336X]
dc.contributor.orcidOlesińska, Magdalena [0000-0001-6969-5179]
dc.contributor.orcidHuang, Zehuan [0000-0003-4111-7064]
dc.contributor.orcidScherman, Oren A [0000-0001-8032-7166]
dc.date.accessioned2022-08-01T23:30:18Z
dc.date.available2022-08-01T23:30:18Z
dc.date.issued2022-08-04
dc.date.updated2022-06-06T11:26:33Z
dc.description.abstractExtended 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.
dc.description.sponsorshipERC Consolidator Grant CAM-RIG 726470
dc.identifier.doi10.17863/CAM.87133
dc.identifier.eissn2041-6539
dc.identifier.issn2041-6520
dc.identifier.urihttps://www.repository.cam.ac.uk/handle/1810/339714
dc.language.isoeng
dc.publisherRoyal Society of Chemistry (RSC)
dc.publisher.departmentDepartment of Chemistry
dc.rightsAttribution 4.0 International
dc.rights.urihttps://creativecommons.org/licenses/by/4.0/
dc.titleSupramolecular encapsulation of redox-active monomers to enable free-radical polymerisation.
dc.typeArticle
dcterms.dateAccepted2022-06-06
prism.publicationNameChem Sci
pubs.funder-project-idEngineering and Physical Sciences Research Council (EP/L027151/1)
pubs.funder-project-idEuropean Research Council (726470)
pubs.funder-project-idRoyal Society (NF170062)
pubs.licence-display-nameApollo Repository Deposit Licence Agreement
pubs.licence-identifierapollo-deposit-licence-2-1
rioxxterms.typeJournal Article/Review
rioxxterms.versionVoR
rioxxterms.versionofrecord10.1039/d2sc02072f

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