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dc.contributor.authorHenwood, Adam Francis
dc.contributor.authorWebster, James
dc.contributor.authorCordes, David Bradford
dc.contributor.authorSlawin, Alexandra Martha Zoya
dc.contributor.authorJacquemin, Denis
dc.contributor.authorZysman-Colman, Eli
dc.date.accessioned2017-05-24T12:30:10Z
dc.date.available2017-05-24T12:30:10Z
dc.date.issued2017-05-12
dc.identifier.citationHenwood , A F , Webster , J , Cordes , D B , Slawin , A M Z , Jacquemin , D & Zysman-Colman , E 2017 , ' Phosphorescent platinum(II) complexes bearing pentafluorosulfanyl substituted cyclometalating ligands ' , RSC Advances , vol. 7 , pp. 25566-25574 . https://doi.org/10.1039/C7RA03190Den
dc.identifier.issn2046-2069
dc.identifier.otherPURE: 249920836
dc.identifier.otherPURE UUID: c988fe26-2a21-4309-9077-9df941e3e5cd
dc.identifier.otherScopus: 85021633899
dc.identifier.otherORCID: /0000-0002-5366-9168/work/33246522
dc.identifier.otherORCID: /0000-0001-7183-6022/work/56639044
dc.identifier.otherORCID: /0000-0002-9527-6418/work/56861339
dc.identifier.otherWOS: 000401535100047
dc.identifier.urihttp://hdl.handle.net/10023/10838
dc.descriptionEZ-C acknowledges the University of St Andrews for financial support. We thank Johnson Matthey and Umicore AG for the gift of materials. We would like to thank the Engineering and Physical Sciences Research Council for financial support for Adam Henwood: EPSRC DTG Grants: EP/J500549/1; EP/K503162/1; EP/L505097/1. We thank the EPSRC UK National Mass Spectrometry Facility at Swansea University for analytical services. DJ thanks the LumoMat RFI project for support. This research used computational resources of (i) the GENCI-CINES/IDRIS; (ii) CCIPL (Centre de Calcul Intensif des Pays de Loire); (iii) a local Troy cluster.en
dc.description.abstractThe first examples of phosphorescent platinum(II) complexes bearing pentafluorosulfanyl (-SF5) substituted cyclometalating ligands (C^N) are reported. These complexes are of the form [Pt(C^N)(pivacac)], where pivacac is 2,2’,6,6’- tetramethylheptane-3,5-dionate. Modifying the phenyl ring of the C^N ligand to incorporate one strongly electron-withdrawing -SF5 group has important effects on the photophysical and electrochemical properties of the complex that are dependent on the regiochemistry of the substituent. In a meta position with respect to the Pt-CC^N bond, the substituent exerts a predominantly stabilising effect on the lowest triplet excited state that red-shifts the emission of the complex compared to the reference [Pt(ppy)(pivacac)], 1 , where ppy is 2-phenylpyridinato. When the -SF5 group is located para to the Pt-CC^N bond, it does not affect the triplet state directly, and the electron-withdrawing group stabilises the metal-based orbitals, resulting in a blue-shift of the emission. In the solid-state all three complexes are mechanochromic, and can display excimeric emission originating from intermolecular π-π* interactions, but the relative emission intensities of the monomeric and dimeric excited states correlate with the steric congestion of the metal centre, and in particular the regiochemistry of the -SF5 group. We correlate these findings with observations in the crystal structures.
dc.language.isoeng
dc.relation.ispartofRSC Advancesen
dc.rightsCopyright 2017 the Authors. This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.en
dc.subjectQD Chemistryen
dc.subjectQH301 Biologyen
dc.subjectDASen
dc.subject.lccQDen
dc.subject.lccQH301en
dc.titlePhosphorescent platinum(II) complexes bearing pentafluorosulfanyl substituted cyclometalating ligandsen
dc.typeJournal articleen
dc.description.versionPublisher PDFen
dc.contributor.institutionUniversity of St Andrews.School of Chemistryen
dc.contributor.institutionUniversity of St Andrews.Organic Semiconductor Centreen
dc.contributor.institutionUniversity of St Andrews.EaSTCHEMen
dc.identifier.doihttps://doi.org/10.1039/C7RA03190D
dc.description.statusPeer revieweden


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