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    Por favor, use este identificador para citar o enlazar este ítem:http://uvadoc.uva.es/handle/10324/21768

    Título
    Higher fluorescence in platinum(IV) orthometallated complexes of perylene imine compared with their platinum(II) or palladium(II) analogues
    Autor
    Exposito Fuertes, José EmilioAutoridad UVA
    Álvarez Paíno, Marta
    Aullón, Gabriel
    Miguel García, Jesús ÁngelAutoridad UVA Orcid
    Espinet Rubio, PabloAutoridad UVA Orcid
    Año del Documento
    2015
    Editorial
    Royal Society of Chemistry
    Descripción
    Producción Científica
    Documento Fuente
    Dalton Transactions, 2015,44, p. 16164-16176
    Resumo
    The reaction of 3-perylenylmethylen-4'-ethylaniline () with [Pt2Me4(μ-SMe2)2] (and subsequent addition of PPh3) or with [Pt2(η(3)-C4H7)2(μ-Cl)2] produced cyclometallated Pt(II) complexes [Pt(C^N)Me(PPh3)] () and, respectively, [Pt2(C^N)2(μ-Cl)2] () (HC^N = 3-C20H11CH[double bond, length as m-dash]NC6H4-p-C2H5), with Pt bound to the ortho site of the perylenyl fragment. From the mononuclear complexes [Pt(C^N)L2] (L2 = acac (); S2COMe (); S2CNEt2 () are easily formed. Oxidative addition of methyl iodide to the square-planar Pt(II) complexes , , and gave the corresponding cyclometallated Pt(IV) compounds [Pt(C^N)L2MeI] , and . The X-ray structures of , , and show that the perylenyl fragment remains essentially flat in and and slightly twisted in . Comparison of the optical properties of these Pt(II) complexes with those reported for similar Pd(II) derivatives reveals that the change of metal exerts a notable influence on the UV-vis spectra. In solution at room temperature, all the Pt complexes exhibit fluorescence associated with the perylene fragment with low emission quantum yields for the Pt(II) complexes (<1%) and remarkably higher emission values for the Pt(IV) complexes: up to 29%, with emission lifetimes of 1-5 ns. Time-dependent density functional theory (TD-DFT) calculations were performed on the perylene imine and on representative complexes [M(C^N)(acac)] (M = Pd, Pt) and [Pt(C^N)(acac)MeI] to analyse the absorption spectra. These calculations support a perylene-dominated intraligand π-π*emissive state based on the HOMO and LUMO orbitals of the perylene chromophore, and a ligand-to-ligand charge-transfer (more intense for the Pt(II) complex) that explains the observed influence of the metal on the absorption properties.
    Materias (normalizadas)
    Chemistry
    ISSN
    1477-9226
    Revisión por pares
    SI
    DOI
    10.1039/C5DT02572A
    Patrocinador
    Ministerio de Economía, Industria y Competitividad (CTQ2014-52796-P)
    Junta de Castilla y León (programa de apoyo a proyectos de investigación – Ref. VA302U13)
    Idioma
    eng
    URI
    http://uvadoc.uva.es/handle/10324/21768
    Derechos
    openAccess
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    Universidad de Valladolid

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