On the Mechanism of d-f Energy Transfer in Ru-II/Ln(III) and Os-II/Ln(III) Dyads: Dexter-Type Energy Transfer Over a Distance of 20 angstrom

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dc.contributor.authorLazarides, T.en
dc.contributor.authorSykes, D.en
dc.contributor.authorFaulkner, S.en
dc.contributor.authorBarbieri, A.en
dc.contributor.authorWard, M. D.en
dc.date.accessioned2015-11-24T16:43:14Z
dc.date.available2015-11-24T16:43:14Z
dc.identifier.issn0947-6539-
dc.identifier.urihttps://olympias.lib.uoi.gr/jspui/handle/123456789/8669
dc.rightsDefault Licence-
dc.subjectbridging ligandsen
dc.subjectenergy transferen
dc.subjectlanthanidesen
dc.subjectluminescenceen
dc.subjectosmiumen
dc.subjectrutheniumen
dc.subjectnear-infrared luminescenceen
dc.subjectcoordination-compoundsen
dc.subjectdinuclear complexesen
dc.subjectphotophysical propertiesen
dc.subjectelectronic excitationen
dc.subjectbinuclear complexesen
dc.subjectquantum yieldsen
dc.subjectyb-iiien
dc.subjectemissionen
dc.subjectsensitizationen
dc.titleOn the Mechanism of d-f Energy Transfer in Ru-II/Ln(III) and Os-II/Ln(III) Dyads: Dexter-Type Energy Transfer Over a Distance of 20 angstromen
heal.abstractWe have used time-resolved luminescence methods to study rates of photoinduced energy transfer (PEnT) from [M(biPY)(3)](2+) (M=Ru, Os) chromophores to Ln(III) ions with low-energy f-f states (Ln=Yb, Nd, Er) in d-f dyads in which the metal fragments are separated by a saturated -CH2CH2- spacer, a P-C6H4 spacer, or a p-(C6H4)(2) spacer. ne finding that clef PEnT is much faster across a conjugated P-C6H4 spacer than it is across a shorter CH2CH2 spacer points unequivocally to Dexter-type energy transfer, involving electronic coupling mediated by the bridging ligand orbitals (superexchange) as the dominant mechanism. Comparison of the distance dependence of the Ru -> Nd energy-transfer rate across different conjugated spacers [P-C6H4 or P-(C6H4)(2) groups] is also consistent with this mechanism. Observation of Ru -> Nd PEnT (as demonstrated by partial quenching of the Ru-II-based (MLCT)-M-3 emission (MLCT= metal-to-ligand charge transfer), and the growth of sensitised Nd-III-based emission at 1050nm) over approximately 20 angstrom by an exchange mechanism is a departure from the normal situation with lanthanides, in which long-range energy transfer often involves through-space Coulombic mechanisms.en
heal.accesscampus-
heal.fullTextAvailabilityTRUE-
heal.identifier.primaryDOI 10.1002/chem.200800600-
heal.identifier.secondary<Go to ISI>://000260703900034-
heal.identifier.secondaryhttp://onlinelibrary.wiley.com/store/10.1002/chem.200800600/asset/9389_ftp.pdf?v=1&t=hmriafzi&s=b37d7d8fc4f260dd56d954f92f75516416b884e5-
heal.journalNameChemistry-a European Journalen
heal.journalTypepeer reviewed-
heal.languageen-
heal.publicationDate2008-
heal.publisherWiley-VCH Verlagen
heal.recordProviderΠανεπιστήμιο Ιωαννίνων. Σχολή Θετικών Επιστημών. Τμήμα Χημείαςel
heal.typejournalArticle-
heal.type.elΆρθρο Περιοδικούel
heal.type.enJournal articleen

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