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.

Proof of polar ejection from the close-binary core of the planetary nebula Abell 63

We present the first detailed kinematical analysis of the planetary nebula Abell 63, which is known to contain the eclipsing close-binary nucleus UU Sge. Abell 63 provides an important test case in investigating the role of close-binary central stars on the evolution of planetary nebulae. Longslit observations were obtained using the Manchester echelle spectrometer combined with the 2.1-m San Pedro Martir Telescope. The spectra reveal that the central bright rim of Abell 63 has a tube-like structure. A deep image shows collimated lobes extending from the nebula, which are shown to be high-velocity outflows. The kinematic ages of the nebular rim and the extended lobes are calculated to be 8400 +/- 500 and 12900 +/- 2800 yr, respectively, which suggests that the lobes were formed at an earlier stage than the nebular rim. This is consistent with expectations that disc-generated jets form immediately after the common envelope phase. A morphological-kinematical model of the central nebula is presented and the best-fitting model is found to have the same inclination as the orbital plane of the central binary system; this is the first proof that a close-binary system directly affects the shaping of its nebula. A Hubble-type flow is well-established in the morphological-kinematical modelling of the observed line profiles and imagery. Two possible formation models for the elongated lobes of Abell 63 are considered, (i) a low-density, pressure-driven jet excavates a cavity in the remnant asymptotic giant branch (AGB) envelope; (ii) high-density bullets form the lobes in a single ballistic ejection event.

Steric effects in the selective hydrogenation of cinnamaldehyde to cinnamyl alcohol using an Ir/C catalyst

The liquid phase selective hydrogenation of cinnamaldehyde to cinnamyl alcohol has been carried out over a graphite-supported iridium catalyst. The effect of reaction parameters such as temperature, pressure, concentration of reactant, the effect of addition of product to the feed and pre-reduction of the catalyst were studied. In situ pre-reduction of the catalyst with hydrogen had a very significant enhancing effect on the conversion of cinnamaldehyde and selectivity of the catalyst to cinnamyl alcohol. Kinetic analysis of the pre-reduced catalyst showed that the reaction is zero order with respect to cinnamaldehyde and first order with respect to hydrogen. The reaction follows an Arrhenius behaviour with an activation energy of 37 kJ mol(-1). Detailed analysis of the reaction showed that hydrogenation of the C=C double bond to give hydrocinnamaldehyde predominantly occurred at low conversions of cinnamaldehyde (

Multiple Evidence for Gold(I)center dot center dot center dot 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 I 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.