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dc.contributor.authorArcher, Stuart A.
dc.contributor.authorKeane, Theo
dc.contributor.authorDelor, Milan
dc.contributor.authorBevon, Elizabeth
dc.contributor.authorAuty, Alexander J.
dc.contributor.authorChekulaev, Dimitri
dc.contributor.authorSazanovich, Igor V.
dc.contributor.authorTowrie, Michael
dc.contributor.authorMeijer, Anthony J. H. M.
dc.contributor.authorWeinstein, Julia A.
dc.date.accessioned2019-01-28T19:13:35Z
dc.date.available2019-01-28T19:13:35Z
dc.date.issued2017-12-27
dc.identifier.citationArcher, S.A., Keane, T., Delor, M., Bevon, E., Auty, A.J., Chekulaev, D., Sazanovich, I.V., Towrie, M., Meijer, A.J. and Weinstein, J.A., (2017). ‘Directly Coupled Versus Spectator Linkers on Diimine PtII Acetylides—Change the Structure, Keep the Function?’. Chemistry–A European Journal, 23(72), pp.18239-18251. DOI: 10.1002/chem.201703989en_US
dc.identifier.issn09476539
dc.identifier.doi10.1002/chem.201703989
dc.identifier.urihttp://hdl.handle.net/10545/623423
dc.description.abstractModification of light‐harvesting units with anchoring groups for surface attachment often compromises light‐harnessing properties. Herein, a series of [donor–acceptor–anchor] platinum(II) diimine (bis‐)acetylides was developed in order to systematically compare the effect of conjugated versus electronically decoupled modes of attachment of protected anchoring groups on the photophysical properties of light‐harvesting units. The first examples of “decoupled” phosphonate diimine PtII complexes are reported, and their properties are compared and contrasted to those of carboxylate analogues studied by a diversity of methods. Ultrafast time‐resolved IR and transient absorption spectroscopy revealed that all complexes have a charge‐transfer (CT) lowest excited state with lifetimes between 2 and 14 ns. Vibrational signatures and dynamics of CT states were identified; the assignment of electronic states and their vibrational origin was aided by TDDFT calculations. Ultrafast energy redistribution accompanied by structural changes was directly captured in the CT states. A significant difference between the structures of the electronic ground and CT excited states, as well as differences in the structural reorganisation in the complexes bearing directly attached or electronically decoupled anchoring groups, was discovered. This work demonstrates that decoupling of the anchoring group from the light‐harvesting core by a saturated spacer is an easy approach to combine surface attachment with high reduction potential and ten times longer lifetime of the CT excited state of the light‐absorbing unit, and retain electron‐transfer photoreactivity essential for light‐harvesting applications.en_US
dc.description.sponsorshipN/Aen_US
dc.language.isoenen_US
dc.publisherWileyen_US
dc.relation.urlhttp://doi.wiley.com/10.1002/chem.201703989en_US
dc.subjectlight harnessingen_US
dc.titleDirectly coupled versus spectator linkers on diimine ptii acetylides—change the structure, keep the functionen_US
dc.typeArticleen_US
dc.contributor.departmentUniversity of Sheffielden_US
dc.contributor.departmentRutherford Appleton Laboratory, Didcoten_US
dc.contributor.departmentUniversity of California, Berkeleyen_US
dc.contributor.departmentMoscow Lomonosov State University, Russiaen_US
dc.identifier.journalChemistry a European Journal.en_US
dc.source.journaltitleChemistry - A European Journal
dc.source.volume23
dc.source.issue72
dc.source.beginpage18239
dc.source.endpage18251
dcterms.dateAccepted2017-10-13
refterms.dateFOA2018-10-13T00:00:00Z


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