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dc.contributor.authorDelor, Milan
dc.contributor.authorArcher, Stuart A.
dc.contributor.authorKeane, Theo
dc.contributor.authorMeijer, Anthony J. H. M.
dc.contributor.authorSazanovich, Igor V.
dc.contributor.authorGreetham, Gregory M.
dc.contributor.authorTowrie, Michael
dc.contributor.authorWeinstein, Julia A.
dc.date.accessioned2018-10-18T15:06:25Z
dc.date.available2018-10-18T15:06:25Z
dc.date.issued2017-06-19
dc.identifier.citationDelor, M. et al. (2017) ‘Directing the path of light-induced electron transfer at a molecular fork using vibrational excitation’, Nature Chemistry, 9 (11), pp. 1099–1104. doi: 10.1038/nchem.2793en
dc.identifier.issn1755-4330
dc.identifier.doi10.1038/nchem.2793
dc.identifier.urihttp://hdl.handle.net/10545/623056
dc.description.abstractUltrafast electron transfer in condensed-phase molecular systems is often strongly coupled to intramolecular vibrations that can promote, suppress and direct electronic processes. Recent experiments exploring this phenomenon proved that light-induced electron transfer can be strongly modulated by vibrational excitation, suggesting a new avenue for active control over molecular function. Here, we achieve the first example of such explicit vibrational control through judicious design of a Pt(II)-acetylide charge-transfer Donor-Bridge-Acceptor-Bridge-Donor “fork” system: asymmetric 13C isotopic labelling of one of the two -C≡C-bridges makes the two parallel and otherwise identical Donor→Acceptor electron-transfer pathways structurally distinct, enabling independent vibrational perturbation of either. Applying an ultrafast UVpump(excitation)-IRpump(perturbation)-IRprobe(monitoring) pulse sequence, we show that the pathway that is vibrationally perturbed during UV-induced electron-transfer is dramatically slowed down compared to its unperturbed counterpart. One can thus choose the dominant electron transfer pathway. The findings deliver a new opportunity for precise perturbative control of electronic energy propagation in molecular devices.
dc.description.sponsorshipEPSRC, STFC, The University of Sheffielden
dc.language.isoenen
dc.publisherSpringeren
dc.relation.urlhttp://www.nature.com/doifinder/10.1038/nchem.2793en
dc.rightsArchived with thanks to Nature Chemistryen
dc.subjectSpectroscopyen
dc.subjectOrganometallic chemistryen
dc.subjectPhysical Chemistryen
dc.subjectOptoelectronicsen
dc.titleDirecting the path of light-induced electron transfer at a molecular fork using vibrational excitation.en
dc.typeArticleen
dc.identifier.eissn1755-4349
dc.contributor.departmentUniversity of Sheffielden
dc.contributor.departmentResearch Complex at Harwellen
dc.identifier.journalNature Chemistryen
refterms.dateFOA2019-02-28T17:38:52Z
html.description.abstractUltrafast electron transfer in condensed-phase molecular systems is often strongly coupled to intramolecular vibrations that can promote, suppress and direct electronic processes. Recent experiments exploring this phenomenon proved that light-induced electron transfer can be strongly modulated by vibrational excitation, suggesting a new avenue for active control over molecular function. Here, we achieve the first example of such explicit vibrational control through judicious design of a Pt(II)-acetylide charge-transfer Donor-Bridge-Acceptor-Bridge-Donor “fork” system: asymmetric 13C isotopic labelling of one of the two -C≡C-bridges makes the two parallel and otherwise identical Donor→Acceptor electron-transfer pathways structurally distinct, enabling independent vibrational perturbation of either. Applying an ultrafast UVpump(excitation)-IRpump(perturbation)-IRprobe(monitoring) pulse sequence, we show that the pathway that is vibrationally perturbed during UV-induced electron-transfer is dramatically slowed down compared to its unperturbed counterpart. One can thus choose the dominant electron transfer pathway. The findings deliver a new opportunity for precise perturbative control of electronic energy propagation in molecular devices.


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