1,4-Bis(2′-pyridylethynyl)benzene as a ligand in heteronuclear gold–thallium complexes. Influence of the ancillary ligands on their optical properties

The reaction of 1,4-bis(2′-pyridylethynyl)benzene (L) with [{Au(C6X5)2}Tl]n affords new heterometallic AuI/TlI complexes with different stoichiometries, structural arrangements and optical properties depending on the halogens present in the aryl group. The chlorinated derivative [{Au(C6Cl5)2}Tl(L)]n (1) displays polymeric chains built thanks to unsupported Au⋯Tl interactions and bridging bidentate ligands between adjacent chains, while in the fluorinated species [{Au(C6F5)2}2Tl2(L)2]n (2), also containing N-donor bridging ligands and Au⋯Tl contacts, polymerization occurs via Tl⋯Caryl non-bonding interactions between neighbouring molecules. The optical properties of 1 and 2 have been studied experimentally and theoretically, concluding that the luminescence of 1 in the solid state has its origin in the Au⋯Tl interactions, and that the Tl⋯Caryl interactions in 2 favour a non-radiative deactivation pathway that avoids luminescence. The strength of the non-bonding interactions present in 1 has also been theoretically studied at the HF and MP2 levels, revealing the metallophilic contact as the strongest one.This work was supported by the D.G.I. (MEC)/FEDER (CTQ2013-48635-C2-2-P).Peer reviewe

Polarized supramolecular aggregates based on luminescent perhalogenated gold derivatives

Reaction of [Au(C6F5)(tht)] (tht = tetrahydrothiophene) with 1,3,5-triaza-7-phosphaadamantane (PTA) and 3,7-diacetyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]-nonane (DAPTA) leads to the formation of [Au(C6F5)(phosph)] (phosph = PTA, 1; phosph = DAPTA, 2). The compounds are slightly soluble in water and aggregate at higher concentrations giving rise to the formation of needle- and rod-like structures (1) and well-organized spherical aggregates (2). Compounds 1 and 2 were reacted with AgPF6 giving rise to the formation in all cases of luminescent water soluble 1:1 Au·Ag heterometallic complexes, as evidenced by X-ray crystal structure determination. The use of different silver salts that differ on the counterion induces changes on the resulting luminescence and aggregation morphology

Silver-based terpyridine complexes as antitumor agents

Silver complexes bearing substituted terpyridine or tetra-2-pyridinylpyrazine ligands have been prepared and structurally characterised. The study of the anticancer properties of silver complexes with this type of ligands is scarce, despite the possibilities of combining the properties of the metal and the ability of the ligands for DNA binding. Here, the antiproliferative activity, stability, CT-DNA binding and mechanism of cell death of these types of derivatives are studied. High cytotoxicity against different tumour cells was observed, and, more important, a great selectivity index has been detected between tumour cells and healthy Lymphocytes T for some of these compounds. The CT-DNA interaction study has shown that these derivatives are be able to interact with CT-DNA via moderate intercalation. Furthermore, cell death studies indicate that these derivatives promote the apoptosis via mitochondrial pathway

Experimental and theoretical evidence of the first Au(I)Bi(III) interaction

3 pages, 3 figures, 1 scheme.-- Published as an advance article on the web 15th Nov. 2006.Complex [Au(C6F5)2][Bi(C6H4CH2NMe2-2)2] 1 displays the first example of an interaction between Au(I) and Bi(III), the nature of which is shown to be consistent with the presence of a high ionic contribution (79%) and a dispersion type (van der Waals) interaction (21%).The D.G.I.(MEC)/FEDER (CTQ2004-05495) project is acknowledged. M. Monge thanks the MEC-UR for his contract ‘‘Ramón y Cajal’’. EC through the Socrates/Erasmus program (M. Nema) and a NATO research fellowship (C. Silvestru) are also acknowledged.Peer reviewe

Synthesis, Photochemical, and Redox Properties of Gold(I) and Gold(III) Pincer Complexes Incorporating a 2,2′:6′,2″-Terpyridine Ligand Framework

Reaction of [Au(C6F5)(tht)] (tht = tetrahydrothiophene) with 2,2′:6′,2″-terpyridine (terpy) leads to complex [Au(C6F5)(η1-terpy)] (1). The chemical oxidation of complex (1) with 2 equiv of [N(C6H4Br-4)3](PF6) or using electrosynthetic techniques affords the Au(III) complex [Au(C6F5)(η3-terpy)](PF6)2 (2). The X-ray diffraction study of complex 2 reveals that the terpyridine acts as tridentate chelate ligand, which leads to a slightly distorted square-planar geometry. Complex 1 displays fluorescence in the solid state at 77 K due to a metal (gold) to ligand (terpy) charge transfer transition, whereas complex 2 displays fluorescence in acetonitrile due to excimer or exciplex formation. Time-dependent density functional theory calculations match the experimental absorption spectra of the synthesized complexes. In order to further probe the frontier orbitals of both complexes and study their redox behavior, each compound was separately characterized using cyclic voltammetry. The bulk electrolysis of a solution of complex 1 was analyzed by spectroscopic methods confirming the electrochemical synthesis of complex 2

Unequivocal experimental evidence of the relationship between emission energies and aurophilic interactions

In this paper we describe experimental evidence of the change in emission energy as a function of gold-gold distance. We have employed a luminescent complex exhibiting an aurophilic interaction, which is weak enough to allow its length to be modified by external pressure, but rigid enough to confer structural stability on the complex. By determining the crystal structures and emission characteristics over a range of pressures, we have identified an exponential relationship between the wavelength of the emitted light and the metal-metal distances under pressure. This result can be indirectly related to the repulsive branch of the fitted function representing the energy of the system at different gold-gold distances. The relativistic nature of gold appears to play an important role in the behaviour of this complex

Síntesis y aplicación de nuevas nanopartículas de plata biocompatibles para el control del crecimiento de bacterias lácticas y acéticas en vinos

Este libro recoge el amplio y significativo elenco de estudios (microbiología) recientemente realizados por los grupos de investigación de la red GIENOL (Grupos de investigación enológica).-- et al.Es bien conocido que la plata tiene propiedades antimicrobianas muy potentes. Actualmente, la nanoplata es el nanomaterial más utilizado, representando aproximadamente la cuarta parte de todos los nanomateriales comercializados en el mercado. El presente trabajo tiene por objetivo explorar la potencial utilización de nuevas nanopartículas de plata como agentes antimicrobianos en enología, como una alternativa al empleo de los sulfitos. En primer lugar, se ha llevado a cabo la síntesis y caracterización de dos materiales de plata: PEG‐Ag NPs 1, nanopartículas sólidas soportadas sobre polietilenglicol, y GSH‐Ag NPs 2, nanopartículas en solución soportadas sobre glutatión. A continuación, se ha evaluado su actividad antimicrobiana frente a un total de 11 especies, que incluyen bacterias lácticas y bacterias acéticas. Se han establecido los parámetros de inhibición bacteriana, comprobándose que los nanomateriales con recubrimientos a base de ambos polímeros solubles (polietilenglicol y glutatión), son capaces de inhibir el crecimiento de ambos tipos de bacterias, y en concreto, el efecto inhibidor sobre las bacterias acéticas, fue superior al del metabisulfito potásico. También se ha estudiado el mecanismo de acción antimicrobiano de las nanopartículas de plata, en el que parece que están implicados cambios en la membrana plasmática de la célula bacteriana con pérdida de la viabilidad celular y de las funciones vitales de la célula.Los autores agradecen la financiación recibida del Ministerio de Economía y Competitividad (MINECO) a través de los proyectos PRI‐PIBAR‐2011‐1358 y AGL2012‐40172‐C02‐01.Peer Reviewe