Syntheses and crystal structures of dinuclear complexes containing d-block and f-block luminophores. Sensitization of NIR luminescence from Yb(III), Nd(III), and Er(III) centers by energy transfer from Re(I)and Pt(II)-bipyrimidine metal centers

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dc.contributor.authorShavaleev, N. M.en
dc.contributor.authorAccorsi, G.en
dc.contributor.authorVirgili, D.en
dc.contributor.authorBell, D. R.en
dc.contributor.authorLazarides, T.en
dc.contributor.authorCalogero, G.en
dc.contributor.authorArmaroli, N.en
dc.contributor.authorWard, M. D.en
dc.date.accessioned2015-11-24T16:48:51Z
dc.date.available2015-11-24T16:48:51Z
dc.identifier.issn0020-1669-
dc.identifier.urihttps://olympias.lib.uoi.gr/jspui/handle/123456789/9379
dc.rightsDefault Licence-
dc.subjectnear-infrared luminescenceen
dc.subjectbis-acetylide complexesen
dc.subjectlanthanide luminescenceen
dc.subjectspectroscopic propertiesen
dc.subjecttransfer mechanismsen
dc.subjectenhanced emissionen
dc.subjectfiber amplifiersen
dc.subjectquantum yieldsen
dc.subjectyb-iiien
dc.subjectytterbiumen
dc.titleSyntheses and crystal structures of dinuclear complexes containing d-block and f-block luminophores. Sensitization of NIR luminescence from Yb(III), Nd(III), and Er(III) centers by energy transfer from Re(I)and Pt(II)-bipyrimidine metal centersen
heal.abstractMononuclear complexes [Re(bpym)(CO)(3)Cl] and [Pt(bpym)(CC-C6H4CF3)(2)] (bpym = 2,2'-bipyrimidine), in which one of the bipyrimidine sites is vacant, have been used as "complex ligands" to prepare heterodinuclear d-f complexes in which a lanthanide tris(1,3-diketonate) unit is attached to the secondary bipyrimidine site to evaluate the ability of d-block chromophores to act as antennae for causing sensitized near-infrared (NIR) luminescence from adjacent lanthanide(III) centers. The two sets of complexes so prepared are [Re(CO)(3)Cl(mu-bpym)Ln(fod)(3)] (abbreviated as Re-Ln; where Ln = Yb, Nd, Er) and [(F3C-C6H4-CC)(2)Pt(mu-bpym)Ln(hfac)(3)] (abbreviated as Pt-Ln; where Ln = Nd, Gd). Members of both series have been structurally characterized; the metal-metal separation across the bipyrimidine bridge is approximate to6.3 Angstrom in each case. In these complexes, the (MLCT)-M-3 (MLCT = metal to ligand charge-transfer) luminescences of the mononuclear [Re(bpym)(CO)(3)Cl] and [Pt(bpym)(CC-C6H4CF3)(2)] complexes are quenched by energy transfer to those lanthanides (Ln = Yb, Nd, Er) that have low-lying f-f states capable of NIR luminescence; as a result, sensitized NIR luminescence is seen from the lanthanide center following excitation of the d-block unit. In the solid state, quenching of the luminescence from the cl-block chromophore is complete, indicating efficient d --> f energy transfer, as a result of the short metal-metal separation across the bipyrimidine bridge. In a CH2CI2 solution, partial dissociation of the dinuclear complexes into the mononuclear units occurs, with the result that some (MLCT)-M-3 luminescence is observed from mononuclear [Re(bpym)(CO)(3)Cl] or [Pt(bpym)(CC-C6H4CF3)(2)] present in the equilibrium mixture. Solution UV-vis and luminescence titrations, carried out by the addition of portions of Ln(fod)(3)(H2O)(2) or Ln(hfaC)(3)(H2O)(2) to the d-block complex ligands, indicate that binding of the lanthanide tris(1,3-diketonate) unit at the secondary bipyrimidine site to give the d-f dinuclear complexes occurs with an association constant of ca. 10(5) M-1.en
heal.accesscampus-
heal.fullTextAvailabilityTRUE-
heal.identifier.primaryDoi 10.1021/Ic048875s-
heal.identifier.secondary<Go to ISI>://000226230600011-
heal.identifier.secondaryhttp://pubs.acs.org/doi/pdfplus/10.1021/ic048875s-
heal.journalNameInorg Chemen
heal.journalTypepeer reviewed-
heal.languageen-
heal.publicationDate2005-
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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