Femtosecond-to-second time-resolved spectroscopy brings unparalleled insight into the life cycle of the versatile manganese photocatalyst [Mn2(CO)10]

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dc.contributor.authorEastwood, Jonathan B.
dc.contributor.authorRankine, Conor D.
dc.contributor.authorBurden, Thomas J.
dc.contributor.authorFrith, Abigail
dc.contributor.authorHammarback, L. Anders
dc.contributor.authorProcacci, Barbara
dc.contributor.authorShaw, Daniel J.
dc.contributor.authorO’Donoghue, Benjamin R.
dc.contributor.authorClark, Ian P.
dc.contributor.authorKaras, Gabriel
dc.contributor.authorMalakar, Partha
dc.contributor.authorGreetham, Gregory M.
dc.contributor.authorTowrie, Michael
dc.contributor.authorHunt, Neil T.
dc.contributor.authorMcGlacken, Gerard P.
dc.contributor.authorFairlamb, Ian J. S.
dc.contributor.authorLynam, Jason M.
dc.contributor.funderEngineering and Physical Sciences Research Council, SRC
dc.contributor.funderScience and Technology Facilities Council, STFC, 1813
dc.contributor.funderLeverhulme Trust, RPG-2021-160
dc.contributor.funderRoyal Society of Chemistry, RSC, EP/W031914/1
dc.contributor.funderDepartment of Chemistry, University of York, EP/N509413/1
dc.contributor.funderIrish Research Council, 21/FFP-A/8784
dc.contributor.funderRoyal Society, INF\R2\202122-INF\R1\221057
dc.date.accessioned2026-05-28T15:50:02Z
dc.date.available2026-05-28T15:50:02Z
dc.date.issued2026-04-08
dc.description.abstractVisible-light-activated radical photoinitiators are pivotal in the efficient construction of complex molecular architectures and the precision synthesis of advanced polymeric materials. At the heart of their function lies the formation of reactive radical species that drive selective homolytic bond cleavage, but elucidating the fundamental mechanisms of these processes is notoriously difficult due to the fleeting nature of key intermediates. In this study, time-resolved infrared (TRIR) spectroscopy provides a powerful window into the complete reaction profile of the versatile photocatalyst [Mn2(CO)10], including the observation of [Mn(O2)(CO)5], which is a long-lived (ms) reservoir of the reactive 17-electron complex [Mn(CO)5]. We give unprecedented structural and mechanistic insights concerning the formation of [Mn(CO)5] in electronically and vibrationally excited states (fs–ps), its quenching by O2 (ns), regeneration of the ground-state catalyst, and C–I bond activation (ms). New avenues for the rational design of next-generation metal–metal photocatalysts are provided, as [Mn(O2)(CO)5] significantly extends the catalyst longevity.en
dc.description.sponsorshipThe authors are grateful to Syngenta, the EPSRC, and the Department of Chemistry at the University of York (iCASE studentship to L.A.H. EP/N509413/1, studentships for J.B.E. and T.J.B.) as well as the Royal Society of Chemistry (Research Enablement Grant to support J.B.E.), the EPSRC (grant number EP/W031914/1), and the Leverhulme Trust (RPG-2021-160, support for B.P.) for funding. The authors thank the STFC for program access to the ULTRA facility (grant number 1813). J.M.L. and I.J.S.F. are both supported by Royal Society Industry Fellowships (INF\R1\221057 and INF\R2\202122 respectively). Funding from Research Ireland (previously the Irish Research Council and Science Foundation Ireland (21/FFP-A/8784)) is also gratefully acknowledged. The authors are particularly grateful to Robin N. Perutz (York) for insightful comments about this study and its findings and to Andrew Orr-Ewing (Bristol) for highlighting the work on the photodissociation of thiophenols.
dc.description.versionPublished Version
dc.format.extent13
dc.format.mimetypeapplication/pdfen
dc.identifier.authororcidEastwood, Jonathan B.
dc.identifier.authororcidRankine, Conor D.
dc.identifier.authororcidBurden, Thomas J.
dc.identifier.authororcidFrith, Abigail
dc.identifier.authororcidHammarback, L. Anders
dc.identifier.authororcidProcacci, Barbara
dc.identifier.authororcidShaw, Daniel J.
dc.identifier.authororcidO’Donoghue, Benjamin R.
dc.identifier.authororcidClark, Ian P.
dc.identifier.authororcidKaras, Gabriel
dc.identifier.authororcidMalakar, Partha
dc.identifier.authororcidGreetham, Gregory M.
dc.identifier.authororcidTowrie, Michael
dc.identifier.authororcidHunt, Neil T.
dc.identifier.authororcidMcGlacken, Gerard P.§0000-0002-7821-0804
dc.identifier.authororcidFairlamb, Ian J. S.
dc.identifier.authororcidLynam, Jason M.
dc.identifier.citationEastwood, J B, Rankine, C D, Burden, T J, Frith, A, Hammarback, L A, Procacci, B, Shaw, D J, O’Donoghue, B R, Clark, I P, Karas, G, Malakar, P, Greetham, G M, Towrie, M, Hunt, N T, McGlacken, G P, Fairlamb, I J S & Lynam, J M 2026, 'Femtosecond-to-second time-resolved spectroscopy brings unparalleled insight into the life cycle of the versatile manganese photocatalyst [Mn2(CO)10]', Journal of the American Chemical Society, vol. 148, no. 15, pp. 15450-15462. https://doi.org/10.1021/jacs.5c16761
dc.identifier.doi10.1021/jacs.5c16761
dc.identifier.endpage15462
dc.identifier.issn0002-7863
dc.identifier.issued15
dc.identifier.journaltitleJournal of the American Chemical Society
dc.identifier.otherRIS: urn:0FE92B9B619D8D864D7131BBAD532BA2
dc.identifier.otherORCID: /0000-0002-7821-0804/work/216088857
dc.identifier.startpage15450
dc.identifier.urihttps://hdl.handle.net/10468/18935
dc.identifier.volume148
dc.language.isoen
dc.publisherAmerican Chemical Society
dc.relation.urihttps://www.scopus.com/pages/publications/105036584304
dc.relation.urihttps://www.scopus.com/pages/publications/105036584304?origin=resultslist
dc.rights© 2026, the Authors. Published by American Chemical Society.
dc.rights.accessrightsopen access
dc.rights.licensenameAttribution 4.0 International
dc.rights.urihttps://creativecommons.org/licenses/by/4.0/
dc.statusPeer reviewed
dc.subjectAmerican Chemical Society
dc.subjectChemical bonds
dc.subjectComplexation
dc.subjectEfficient construction
dc.subjectExcited states
dc.subjectFemtoseconds
dc.subjectFree radical reactions
dc.subjectGround state
dc.subjectLife cycle
dc.subjectManganese
dc.subjectMolecular architecture
dc.subjectPhotocatalysts
dc.subjectRadical photoinitiators
dc.subjectRadical species
dc.subjectReactive radicals
dc.subjectTime-resolved spectroscopy
dc.subjectVisible light
dc.subject[Chemistry]
dc.subject]+ catalyst
dc.titleFemtosecond-to-second time-resolved spectroscopy brings unparalleled insight into the life cycle of the versatile manganese photocatalyst [Mn2(CO)10]en
dc.typeArticle (peer-reviewed)
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