Structural and photophysical properties of adducts of [Ru(bipy)(CN)(4)](2-) with different metal cations: Metallochromism and its use in switching photoinduced energy transfer

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dc.contributor.authorLazarides, T.en
dc.contributor.authorEasun, T. L.en
dc.contributor.authorVeyne-Marti, C.en
dc.contributor.authorAlsindi, W. Z.en
dc.contributor.authorGeorge, M. W.en
dc.contributor.authorDeppermann, N.en
dc.contributor.authorHunter, C. A.en
dc.contributor.authorAdams, H.en
dc.contributor.authorWard, M. D.en
dc.date.accessioned2015-11-24T16:47:57Z
dc.date.available2015-11-24T16:47:57Z
dc.identifier.issn0002-7863-
dc.identifier.urihttps://olympias.lib.uoi.gr/jspui/handle/123456789/9260
dc.rightsDefault Licence-
dc.subjectnear-infrared luminescenceen
dc.subjectlanthanide(iii) cationsen
dc.subjectmolecular electronicsen
dc.subjectcomplexesen
dc.subjectcyanideen
dc.subjectanionsen
dc.subjectchemistryen
dc.subjectligandsen
dc.subjectroutesen
dc.subjectelectrochemistryen
dc.titleStructural and photophysical properties of adducts of [Ru(bipy)(CN)(4)](2-) with different metal cations: Metallochromism and its use in switching photoinduced energy transferen
heal.abstractWe show in this paper how the (MLCT)-M-3 luminescence of [Ru(bipy)(CN)(4)](2-), which is known to be highly solvent-dependent, may be varied over a much wider range than can be achieved by solvent effects, by interaction of the externally directed cyanide ligands with additional metal cations both in the solid state and in solution. A series of crystallographic studies of [Ru(bipy)(CN)(4)](2-) salts with different metal cations Mn+ (Li+, Na+, K+, mixed Li+/K+, Cs+, and Ba2+) shows how the cyanide/Mn+ interaction varies from the conventional "end-on" with the more Lewis-acidic cations (Li+, Ba2+) to the more unusual "side-on" interaction with the softer metal cations (K+, Cs+). The solid-state luminescence intensity and lifetime of these salts is highly dependent on the nature of the cation, with Cs+ affording the weakest luminescence and Ba2+ the strongest. A series of titrations of the more soluble derivative [Ru((t)Bu(2)bipy)(CN)(4)](2-) in MeCN with a range of metal salts showed how the cyanide/Mn+ association results in a substantial blue-shift of the (MLCT)-M-1 absorptions, and (MLCT)-M-3 energies, intensities, and lifetimes, with the complex varying from essentially non-luminescent in the absence of metal cation to showing strong (phi = 0.07), long-lived (1.4 mu s), and high-energy (583 nm) luminescence in the presence of Ba2+. This modulation of the (MLCT)-M-3 energy, over a range of about 6000 cm(-1) depending on the added cation, could be used to reverse the direction of photoinduced energy transfer in a dyad containing covalently linked [Ru(bipy)(3)](2+) and [Ru(bipy)(CN)(4)](2-) termini. In the absence of a metal cation, the [Ru(bipy)(CN)(4)](2-) terminus has the lower (MLCT)-M-3 energy and thereby quenches the [Ru(bipy)(3)](2+)-based luminescence; in the presence of Ba2+ ions, the (MLCT)-M-3 energy of the [Ru(bipy)(CN)(4)](2-) terminus is raised above that of the [Ru(bipy)(3)](2+) terminus, resulting in energy transfer to and sensitized emission from the latter.en
heal.accesscampus-
heal.fullTextAvailabilityTRUE-
heal.identifier.primaryDoi 10.1021/Ja068436n-
heal.identifier.secondary<Go to ISI>://000245241600054-
heal.identifier.secondaryhttp://pubs.acs.org/doi/pdfplus/10.1021/ja068436n-
heal.journalNameJ Am Chem Socen
heal.journalTypepeer reviewed-
heal.languageen-
heal.publicationDate2007-
heal.publisherAmerican Chemical Societyen
heal.recordProviderΠανεπιστήμιο Ιωαννίνων. Σχολή Θετικών Επιστημών. Τμήμα Χημείαςel
heal.typejournalArticle-
heal.type.elΆρθρο Περιοδικούel
heal.type.enJournal articleen

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