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    Por favor, use este identificador para citar o enlazar este ítem:http://uvadoc.uva.es/handle/10324/42792

    Título
    Fluorescent perylenylpyridine complexes: an experimental and theoretical study
    Autor
    Exposito Fuertes, José EmilioAutoridad UVA
    Aullón, Gabriel
    Bardají Luna, ManuelAutoridad UVA Orcid
    Miguel García, Jesús ÁngelAutoridad UVA Orcid
    Espinet Rubio, PabloAutoridad UVA Orcid
    Año del Documento
    2020
    Editorial
    Royal Society of Chemistry
    Descripción
    Producción Científica
    Documento Fuente
    Dalton Transactions, Issue 49, 2020, 13326-13338
    Abstract
    The perylene derivative 2-(3-perylenyl)-4-methylpyridine (HPerPy) was prepared and used to synthesize [Ag(HPerPy)(PPh3)(OClO3)], with the perylene ligand bonded to the metal centre only by the pyridine nitrogen. The treatment of HPerPy with [Pd(OAc)2] in methanol or acetic acid led to acetate bridged dimers (μ-OOCCH3)2[Pd(PerPy)]2, six-membered or five-membered cycled at the perylenyl fragment. Substitution reactions afforded mononuclear compounds [Pd(PerPy)(acac)] (six-member or five-member cycled) and [Pd(PerPy)(S2COMe)] (six-member or five-member cycled). The reaction of HPerPy with a platinum(II) fragment led to a five-membered cyclometallated Pt(II) complex [Pt(PerPy)(acac)]. The oxidative addition with MeI gave the corresponding cyclometallated Pt(IV) compound [Pt(PerPy)(acac)MeI]. X-ray single crystal studies of compounds [Ag(HPerPy)(PPh3)(OClO3)], (μ-OOCCH3)2[Pd(PerPy)]2-five-membered, [Pd(PerPy)(acac)]-six-membered, [Pd(PerPy)(S2COMe)]-five-membered, [Pt(PerPy)(acac)]-five-membered, and [Pt(PerPy)(acac)MeI]-five-membered confirmed the proposed structures. The UV-Vis spectra show one intense absorption with vibronic coupling in the visible region with maxima in the range of 448–519 nm. DFT calculations were carried out for the absorption spectra of the HPerPy molecule and representative complexes [M(PerPy)(acac)] (M: Pd, Pt; five and six-membered isomers) and [Pt(PerPy)(acac)MeI], showing that the lowest energy most intense transition in the complexes corresponds to the HOMO → LUMO transition in the perylene moiety, although affected by the metallacycle size and the metal nature. All the compounds are fluorescent in solution, due to the perylene fragment. The emission spectra display maxima in the range of 468–549 nm, with quantum yields from 1.1 to 82%. The attenuation of the intensity of fluorescence by the presence of heavy atoms and the formation of metallacycles has been experimentally determined and sequenced.
    Palabras Clave
    Perileno
    Perylene
    ISSN
    1477-9226
    Revisión por pares
    SI
    DOI
    10.1039/D0DT02494E
    Patrocinador
    Ministerio de Economía, Industria y Competitividad (Project CTQ2017-89217-P)
    Junta de Castilla y León (Project VA038G18)
    Version del Editor
    https://pubs.rsc.org/en/content/articlelanding/2020/DT/D0DT02494E#!divAbstract
    Propietario de los Derechos
    © 2020 Royal Society of Chemistry
    Idioma
    eng
    URI
    http://uvadoc.uva.es/handle/10324/42792
    Tipo de versión
    info:eu-repo/semantics/acceptedVersion
    Derechos
    openAccess
    Collections
    • CINQUIMA - Artículos de revista [162]
    • DEP63 - Artículos de revista [322]
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    Attribution-NonCommercial-NoDerivatives 4.0 InternacionalExcept where otherwise noted, this item's license is described as Attribution-NonCommercial-NoDerivatives 4.0 Internacional

    Universidad de Valladolid

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