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dc.contributor.authorGoia, Sofia
dc.contributor.authorTurner, Matthew AP
dc.contributor.authorWoolley, Jack M
dc.contributor.authorHorbury, Michael D
dc.contributor.authorBorrill, Alexandra J
dc.contributor.authorTully, Joshua J
dc.contributor.authorCobb, Samuel J
dc.contributor.authorStaniforth, Michael
dc.contributor.authorHine, Nicholas DM
dc.contributor.authorBurriss, Adam
dc.contributor.authorMacpherson, Julie V
dc.contributor.authorRobinson, Ben R
dc.contributor.authorStavros, Vasilios G
dc.date.accessioned2022-03-13T02:03:24Z
dc.date.available2022-03-13T02:03:24Z
dc.date.issued2022-01-05
dc.identifier.issn2041-6520
dc.identifier.otherPMC8730129
dc.identifier.other35126981
dc.identifier.urihttps://www.repository.cam.ac.uk/handle/1810/334929
dc.description.abstractMany photoactivated processes involve a change in oxidation state during the reaction pathway and formation of highly reactive photoactivated species. Isolating these reactive species and studying their early-stage femtosecond to nanosecond (fs-ns) photodynamics can be challenging. Here we introduce a combined ultrafast transient absorption-spectroelectrochemistry (TA-SEC) approach using freestanding boron doped diamond (BDD) mesh electrodes, which also extends the time domain of conventional spectrochemical measurements. The BDD electrodes offer a wide solvent window, low background currents, and a tuneable mesh size which minimises light scattering from the electrode itself. Importantly, reactive intermediates are generated electrochemically, via oxidation/reduction of the starting stable species, enabling their dynamic interrogation using ultrafast TA-SEC, through which the early stages of the photoinduced relaxation mechanisms are elucidated. As a model system, we investigate the ultrafast spectroscopy of both anthraquinone-2-sulfonate (AQS) and its less stable counterpart, anthrahydroquinone-2-sulfonate (AH2QS). This is achieved by generating AH2QS in situ from AQS via electrochemical means, whilst simultaneously probing the associated early-stage photoinduced dynamical processes. Using this approach we unravel the relaxation mechanisms occurring in the first 2.5 ns, following absorption of ultraviolet radiation; for AQS as an extension to previous studies, and for the first time for AH2QS. AQS relaxation occurs via formation of triplet states, with some of these states interacting with the buffered solution to form a transient species within approximately 600 ps. In contrast, all AH2QS undergoes excited-state single proton transfer with the buffered solution, resulting in formation of ground state AHQS- within approximately 150 ps.
dc.languageeng
dc.publisherRoyal Society of Chemistry (RSC)
dc.rightsAttribution 4.0 International
dc.rights.urihttps://creativecommons.org/licenses/by/4.0/
dc.sourcenlmid: 101545951
dc.sourceessn: 2041-6539
dc.titleUltrafast transient absorption spectroelectrochemistry: femtosecond to nanosecond excited-state relaxation dynamics of the individual components of an anthraquinone redox couple.
dc.typeArticle
dc.date.updated2022-03-13T02:03:23Z
prism.endingPage496
prism.issueIdentifier2
prism.publicationNameChem Sci
prism.startingPage486
prism.volume13
dc.identifier.doi10.17863/CAM.82367
dcterms.dateAccepted2021-12-08
rioxxterms.versionofrecord10.1039/d1sc04993c
rioxxterms.versionVoR
rioxxterms.licenseref.urihttps://creativecommons.org/licenses/by/4.0/
dc.contributor.orcidGoia, Sofia [0000-0002-4492-0410]
dc.contributor.orcidWoolley, Jack M [0000-0002-3893-3880]
dc.contributor.orcidHorbury, Michael D [0000-0001-8235-8142]
dc.contributor.orcidBorrill, Alexandra J [0000-0001-5495-0181]
dc.contributor.orcidTully, Joshua J [0000-0002-9584-0437]
dc.contributor.orcidCobb, Samuel J [0000-0001-5015-8090]
dc.contributor.orcidHine, Nicholas DM [0000-0001-5613-3679]
dc.contributor.orcidMacpherson, Julie V [0000-0002-4249-8383]
dc.contributor.orcidStavros, Vasilios G [0000-0002-6828-958X]
dc.identifier.eissn2041-6539
cam.issuedOnline2021-12-17


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Attribution 4.0 International
Except where otherwise noted, this item's licence is described as Attribution 4.0 International