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Luminescent Benzoquinolate-Isocyanide Platinum(II) Complexes: Effect of Pt⋅⋅⋅Pt and π⋅⋅⋅π Interactions on their Photophysical Properties

AuthorsForniés, Juan ; Sicilia, Violeta ; Borja, Pilar ; Casas, José M. ; Díez, Alvaro; Lalinde, Elena; Larraz, Carmen; Martín, Antonio ; Moreno, M. Teresa
Issue Date2012
CitationChemistry - An Asian Journal 7(12): 2813-2823 (2012)
AbstractThe neutral compounds [Pt(bzq)(CN)(CNR)] (R=tBu (1), Xyl (2), 2-Np (3); bzq= benzoquinolate, Xyl=2,6-dimethylphenyl, 2-Np=2-napthyl) were isolated as the pure isomers with a trans-Cbzq,CNR configuration, as confirmed by 13C{1H} NMR spectroscopy in the isotopically marked [Pt(bzq)(13CN)(CNR)] (R=tBu (1′), Xyl (2′), 2-Np (3′)) derivatives (δ13CCN≈110 ppm; 1J(Pt,13C)≈1425 Hz]. By contrast, complex [Pt(bzq)(C≡CPh)(CNXyl)] (4) with a trans-Nbzq,CNR configuration, has been selectively isolated from [Pt(bzq)Cl(CNXyl)] (trans-Nbzq,CNR) using Sonogashira conditions. X-ray diffraction studies reveal that while 1 adopts a columnar-stacked chain structure with Pt–Pt distances of 3.371(1) Å and significant π⋅⋅⋅π interactions (3.262 Å), complex 2 forms dimers supported only by short Pt⋅⋅⋅Pt (3.370(1) Å) interactions. In complex 4 the packing is directed by weak bzq⋅⋅⋅Xyl and bzq⋅⋅⋅C≡E (C, N) interactions. In solid state at room temperature, compounds 1 and 2 both show a bright red emission (ϕ=42.1 % 1, 57.6 % 2). Luminescence properties in the solid state at 77 K and concentration-dependent emission studies in CH2Cl2 at 298 K and at 77 K are also reported for 1-4. Los compuestos neutros [Pt(bzq)(CN)(CNR)] [R=tBu 1, Xyl 2, 2-Np 3] fueron aislados como isómeros puros con una configuración trans-Cbzq,CNR, como se confirmó por espectroscopía de RMN de 13C{1H} de los derivados marcados isotópicamente [Pt(bzq)(13CN)(CNR)] [R=tBu 1′, Xyl 2′, 2-Np 3′] [δ13CCN≈110 ppm; 1J(Pt,13C)≈1425 Hz]. Por el contrario, el complejo [Pt(bzq)(C≡CPh)(CNXyl)] (4) con una configuración trans-Nbzq,CNR, ha sido aislado selectivamente a partir de [Pt(bzq)Cl(CNXyl)] (trans-Nbzq,CNR) empleando la reacción de Sonogashira. Los estudios de difracción de rayos X revelan que mientras 1 adopta una estructura de apilamiento en columna con distancias Pt-Pt de 3.371(1) Å e importantes interacciones π⋅⋅⋅π (3.262 Å), el complejo 2 forma dímeros unidos solamente por interacciones Pt⋅⋅⋅Pt [3.370(1) Å]. En el complejo 4 el empaquetamiento está dirigido por débiles interacciones bzq⋅⋅⋅Xyl y bzq⋅⋅⋅C≡E (C, N). En estado sólido a temperatura ambiente los compuestos 1 y 2 muestran una emisión roja muy intensa (ϕ=57.6 % 2, 42.1 % 1). Se describen también las propiedades luminiscentes en estado sólido a 77 K y en CH2Cl2 en diversas concentraciones a 298 K y a 77 K de 1–4.
Identifiersdoi: 10.1002/asia.201200585
issn: 1861-4728
e-issn: 1861-471X
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