M. Cristina Lagunas

Effects of diphosphine structure on aurophilicity and luminescence in Au(I) complexes

The effects of diphosphine flexibility and bite angle on the structures and luminescence properties of Au(I) complexes have been investigated. A range of diphosphines based on heteroaromatic backbones [bis(2-diphenylphosphino)phenylether (dpephos), 9,9-dimethyl-4,5-bis(diphenylphosphino)xanthene (xantphos), and 4,6-bis(diphenylphosphino)dibenzofuran (dbfphos)] has been used to prepare mono- and digold derivatives. A clear relationship between the presence of aurophilic contacts and the emission properties of dinuclear complexes has been observed, with one of the complexes studied, [Au(2)Cl(2)(micro-xantphos)], exhibiting luminescence thermochromism.

Electrochemistry of Sulfur and Polysulfides in Ionic Liquids

The electrochemistry of elemental sulfur (S(8)) and the polysulfides Na(2)S(4) and Na(2)S(6) has been studied for the first time in nonchloroaluminate ionic liquids. The cyclic voltammetry of S(8) in the ionic liquids is different to the behavior reported in some organic solvents, with two reductions and one oxidation peak observed. Supported by in situ UV-vis spectro-electrochemical experiments, the main reduction products of S(8) in [C(4)mim][DCA] ([C(4)mim] = 1-butyl-3-methylimidazolium; DCA = dicyanamide) have been identified as S(6)(2-) and S(4)(2-), and plausible pathways for the formation of these species are proposed. Dissociation and/or disproportionation of the polyanions S(6)(2-) and S(4)(2-) appears to be slow in the ionic liquid, with only small amounts of the blue radical species S(3)(•-) formed in the solutions at r.t., in contrast with that observed in most molecular solvents.

Preparation of AgX (X = Cl, I) nanoparticles using ionic liquids

Nanoparticles of silver halides have been prepared by mixing silver halide powder with a single liquid phase consisting of an ionic liquid, isooctane, n-decanol and water. Much higher nanoparticle concentrations may be formed with ionic liquids using this new simple method than are found with conventionally applied surfactants. This method also emphasizes the applicability of ionic liquids as versatile components in microemulsions and as solvents for the synthesis of nanomaterials. The effect on the nanoparticles of changing the composition of the liquid mixtures and the nature of the ionic liquid is analysed. High nanoparticle concentrations were only found with chloride based ionic liquids, indicating the importance of the ionic liquid anion in the mechanism of the reaction.

Synthesis of gold-silver luminescent honeycomb aggregates by both solvent-based and solvent-free methods

Heterometallic clusters with strong luminescence have been synthesized (see picture: Au(C≡CPh)(2)yellow-red, Ag(2)blue, Ored) from the metalloligand unit [Au(C≡CPh)PPh(3) ] (yellow/red bars) by using both standard solvent-based and solvent-free reactions. The aggregates are stabilized only by acetylide-metal or metal-metal interactions, and their nuclearity is controlled through the addition of different donor ligands.

Multiple Evidence for Gold(I)⋅⋅⋅Silver(I) Interactions in Solution

[AuAg3(C6F5)(CF3CO2)3(CH2PPh3)]n (2) was prepared by reaction of [Au(C6F5)(CH2PPh3)] (1) and [Ag(CF3CO2)] (1:3). The crystal structures of complexes 1 and 2 were determined by X-ray diffraction, and the latter shows a polymeric 2D arrangement built by Au...Ag, Ag...Ag, and Ag...O contacts. The metallophilic interactions observed in 2 in the solid state seem to be preserved in concentrated THF solutions, as suggested by EXAFS, pulsed-gradient spin-echo NMR, and photophysical studies, which showed that the structural motif [AuAg3(C6F5)(CF3CO2)3(CH2PPh3)] is maintained under such conditions. Time-dependent DFT calculations agree with the experimental photophysical energies and suggest a metal-to-ligand charge-transfer phosphorescence process. Ab initio calculations give an estimated interaction energy of around 60 kJ mol(-1) for each Au...Ag interaction.

Factors affecting luminescence and aurophilicity on digold(I) complexes and their potential as cation probes

In the last few years we have analysed the factors that affect the structures and luminescence properties of Au(I) compounds, specifically in relation with the presence of aurophilic contacts and their application as cation probes. EXAFS studies have allowed us to obtain for the first time direct structural data of dissolved Au(I) compounds. An overview of the work reported to date is presented here. The optical properties of complex [Au2Cl2(μ-dpephos)] (dpephos =bis(2-diphenylphosphino) phenylether, 1) have been revisited and new results are now included. New aspects on the use of the complexes as Ag(I) probes are also discussed.

A new approach for the detection of ethylene using silica-supported palladium complexes

The coordination of olefins to square-planar Pd(II) and Pt(II) complexes containing 2,9-dimethylphenanthroline ( L1) often involves a change of color associated with a change of geometry at the metal center. In order to obtain suitable colorimetric detectors for ethylene gas, a series of new Pd(II) and Pt(II) compounds with a range of 2,9-disubstituted phenanthroline ligands [2,9-di- n-butyl-1,10-phenanthroline ( L2), 2,9-di- s-butyl-1,10-phenanthroline ( L3), 2,9-diphenyl-1,10-phenanthroline ( L4), and 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (bathocuproine, L5)] have been prepared and their reactivity toward ethylene investigated both in solution and after depositing the detector compounds on a variety of solid supports. The Pd(II) complex [PdCl 2( L2)] supported on silica undergoes a clear color change upon exposure to ethylene, while remaining stable toward air and water, and forms the basis for new simple colorimetric detectors with potential applications in ethylene pipe-leak detection and the monitoring of fruit ripening. Encouragingly, the detector is able to discriminate between fruit at different stages of ripening. The response of the detector to other volatiles was also examined, and specific color changes were also observed upon exposure to aromatic acetylenes. The crystal structures of four new derivatives, including the ethylene-Pt(II) complex [PtCl 2(C 2H 4)( L2)], are also described.

Chromo- and fluorogenic Organometallic Sensors

Compounds that change their absorption and/or emission properties in the presence of a target ion or molecule have been studied for many years as the basis for optical sensing. Within this group of compounds, a variety of organometallic complexes have been proposed for the detection of a wide range of analytes such as cations (including H+), anions, gases (e.g. O2, SO2, organic vapours), small organic molecules, and large biomolecules (e.g. proteins, DNA). This chapter focuses on work reported within the last few years in the area of organometallic sensors. Some of the most extensively studied systems incorporate metal moieties with intense long-lived metal-to-ligand charge transfer (MLCT) excited states as the reporter or indicator unit, such as fac-tricarbonyl Re(I) complexes, cyclometallated Ir(III) species, and diimine Ru(II) or Os(II) derivatives. Other commonly used organometallic sensors are based on Pt-alkynyls and ferrocene fragments. To these reporters, an appropriate recognition or analyte-binding unit is usually attached so that a detectable modification on the colour and/or the emission of the complex occurs upon binding of the analyte. Examples of recognition sites include macrocycles for the binding of cations, H-bonding units selective to specific anions, and DNA intercalating fragments. A different approach is used for the detection of some gases or vapours, where the sensors response is associated with changes in the crystal packing of the complex on absorption of the gas, or to direct coordination of the analyte to the metal centre.

Electrochemistry of Hg(II) Salts in Room-Temperature Ionic Liquids

The electrochemistry of HgCl(2) and [Hg(NTf(2))(2)] ([NTf(2)](-)=bis-{(trifluoromethyl)sulfonyl}imide) has been studied in room temperature ionic liquids. It has been found that the cyclic voltammetry of Hg(II) is strongly dependent on a number of factors (e.g., concentration, anions present in the mixture, and nature of the working electrode) and differs from that found in other media. Depending on conditions, the cyclic voltammetry of Hg(II) can give rise to one, two, or four reduction peaks, whereas the reverse oxidative scans show two to four peaks. Diffuse reflectance UV-vis spectroscopy and X-ray powder diffraction have been used to aid the assignment of the voltammetric waves.