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Novel luminescent mixed-metal Pt---------Tl-alkynyl-based complexes: The role of the alkynyl substituent in metallophilic and 2(Tl)-bonding interactions

AuthorsBerenguer, Jesús R.; Forniés, Juan CSIC; Gil, Belén; Lalinde, Elena
Cluster compounds
Columnar structure
Issue DateJan-2006
CitationChemistry - a European Journal 12(3): 785-795 (2006)
Abstract[EN] A novel series of [PtTl2(CCR)4]n (n=2, R=4-CH3C6H4 (Tol) 1, 1-naphthyl (Np) 2; n=, R=4-CF3C6H4 (TolF) 3) complexes has been synthesized by neutralization reactions between the previously reported [Pt(CCR)4]2- (R=Tol, TolF) or novel (NBu4)2[Pt(CCNp)4] platinum precursors and TlI (TlNO3 or TlPF6). The crystal structures of [Pt2Tl4(CCTol)8]4 acetone, 14 acetone, [Pt2Tl4(CCNp)8]3 acetone1/3 H2O, 23 acetone 1/3 H2O and [{PtTl2(CCTolF)4}(acetone)S] (S=acetone 3 a; dioxane 3 b) have been solved by X-ray diffraction studies. Interestingly, whereas in the tolyl (1) and naphthyl (2) derivatives, the thallium centers exhibit a bonding preference for the electron-rich alkyne entities to yield crystal lattices based on sandwich hexanuclear [Pt2Tl4(CCR)8] clusters (with additional Tlacetone (1) or Tlnaphthyl (2) secondary interactions), in the C6H4CF3 (TolF) derivatives 3 a and 3 b the basic PtII center forms two unsupported PtTl bonds. As a consequence 3 a and 3 b form an extended columnar structure based on trimetallic slipped PtTl2(CCTolF)4 units that are connected through secondary Tl(2-acetylenic) interactions. The luminescent properties of these complexes, which in solution (blue; CH2Cl2 1,2; acetone 3) are very different to those in solid state (orange), have been studied. Curiously, solid-state emission from 1 is dependent on the presence of acetone (green) and its crystallinity. On the other hand, while a powder sample of 3 is pale yellow and displays blue (457 nm) and orange (611 nm) emissions, the corresponding pellets (KBr, solid) of 3, or the fine powder obtained by grinding, are orange and only exhibit a very intense orange emission (590 nm).
[ES] Se ha sintetizado una nueva serie de complejos [PtTl2(CCR)4]n (n=2, R=4-CH3C6H4 (Tol) 1, 1-naftil (Np) 2; n=, R=4-CF3C6H4 (TolF) 3) por neutralización entre TlI (TlNO3 o TlPF6) y los sustratos de platino [Pt(CCR)4]2- (R=Tol, TolF) ya descritos o el nuevo (NBu4)2[Pt(CCNp)4]. Asimismo, se han resuelto, mediante estudios de difracción de rayos-X, las estructuras cristalinas de [Pt2Tl4(CCTol)8]4 acetona, 14 acetona, [Pt2Tl4(CCNp)8]3 acetona1/3 H2O, 23 acetona1/3 H2O, y [{PtTl2(CCTolF)4}(acetona)S] (S=acetona 3 a; dioxano 3 b). Curiosamente, mientras que en los derivados de tolilo (1) y naftilo (2), los centros metálicos de talio exhiben una clara preferencia de enlace hacia los fragmentos básicos acetilénicos, dando lugar a redes cristalinas basadas en oligómeros hexanucleares de tipo sándwich [Pt2Tl4(CCR)8] (con interacciones secundarias adicionales Tlacetona, 1, o Tlnaftilo, 2), en los derivados con C6H4CF3 (TolF), 3 a y 3 b, el centro básico de PtII forma dos enlaces Pt-Tl no soportados. Como consecuencia, 3 a y 3 b forman una estructura columnar extendida, basada en la conexión, a través de interacciones secundarias Tl2(acetileno), de unidades trimetálicas PtTl2(CCTolF)4 desplazadas entre sí. Además, se han estudiado las propiedades luminiscentes, que difieren mucho en disolución (azul; CH2Cl2 1,2; acetona 3) a estado sólido (naranja). De manera interesante, la emisión de 1 en estado sólido depende de la presencia de acetona (verde), así como de su cristalinidad. Por otro lado, mientras que una muestra pulverulenta de 3 es de color amarillo pálido y muestra emisiones en el azul (457 nm) y naranja (611 nm), las pastillas obtenidas por presión (KBr o sólido puro), o, incluso, el polvo fino obtenido por molturación, son de color naranja y exhiben solamente una emisión intensa en el naranja (590 nm).
Description11 pages, 5 tables, 8 figures, 1 scheme.-- Supporting information for this article is available on: or from the author.-- Published Online: 30 Sep 2005.
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