Ring-opening polymerisation of silver-diphosphine [M2L3] coordination cages to give [M2L3](infinity) coordination polymers

[M2L3] coordination cages and linear [M2L3]infinity polymers of the rigid, bridging diphosphines bis(diphenylphosphino)acetylene (dppa) and trans-1,2-bis(diphenylphosphino)ethylene (dppet) with silver(I) salts have been investigated in the solution and solid states. Unlike flexible diphosphines, 1:1 dppa/AgX mixtures do not selectively form discrete [Ag2(diphos)2(X)2] macrocycles; instead dynamic mixtures of one-, two- and three-coordinate complexes are formed. However, 3:2 dppa/AgX ratios (X = SbF6. BF4, O3SCF3 or NO3) do lead selectively to new [M2L3] triply bridged cage complexes [Ag2(dppa)3(X)2] 1a-d (X = SbF6 a, BF4 b, O3SCF3 c, NO3 d), which do not exhibit Ag-P bond dissociation at room temperature on the NMR time scale (121 MHz). Complexes la-d were characterised by X-ray crystallography and were found to have small internal cavities, helical conformations and multiple intramolecular aromatic interactions. The nucleophilicity of the anion subtly influences the cage shape: Increasing nucleophilicity from SbF6 (1a) through BF4 (1b) and O3SCF3 (1c) to NO3 (1d) increases the pyramidal distortion at the AgP3 centres, stretching the cage framework (with Ag...Ag distances increasing from 5.48 in 1a to 6.21 A in 1d) and giving thinner internal cavities. Crystal packing strongly affected the size of the helical twist angle, and no correlation between this parameter and the Ag-Ag distance was observed. When crystalline 1c was stored in its supernatant for 16 weeks, conversion occured to the isostoichiometric [M2L3]infinity coordination polymer [Ag(dppa)2Ag(dppa)(O3SCF3)2]infinity (1c'). X-ray crystallography revealed a structure with ten-membered Ag2(dppa)2 rings linked into infinite one-dimensional chains by a third dppa unit. The clear structural relationship between this polymer and the precursor cage 1c suggests a novel example of ring-opening polymerisation. With dppet, evidence for discrete [M2L3] cages was also found in solution, although 31P NMR spectroscopy suggested some Ag-P bond dissociation. On crystallisation, only the corresponding ring-opened polymeric structures [M2L3]infinity could be obtained. This may be because the greater steric bulk of dppet versus dppa destabilises the cage and favours the ring-opening polymerisation.

A peculiar metal-rich star, HD 135485

Local thermodynamic equilibrium (LTE) absolute and differential abundances are presented for a peculiar metal-rich B-type star, HD 135485. These suggest that HD 135485 has a general enrichment of similar to0.5 dex in all the metals observed (C, N, O, Ne, Mg, Al, Si, P, S, Cl, Ar, Sc, Ti, Cr, Mn, Fe and Sr), except for nickel. The helium enhancement and hence hydrogen deficiency can account for less than or equal to 0.2 dex of this enhancement of metals, with the additional enhancement probably being representative of the progenitor gas. However, some of the metals appear to have greater enhancements, which may have occurred during the star's evolution. The significantly larger nitrogen abundance coupled with a modest helium enhancement observed in HD 135485 indicates that carbon- nitrogen (CN) processed material has possibly contaminated the stellar surface. Neon and carbon enhancements may indicate that helium core flashes have also occurred in HD 135485. Some of the iron-group elements (viz. Mn and Ni) appear to have similar abundance patterns to that of silicon Ap stars, but it is uncertain how these abundance patterns formed if they were not present in the progenitor gas. From a kinematical investigation it is unclear whether this star formed in a metal-rich region as implied by its chemical composition. From its position in the Hertzsprung-Russell diagram, HD 135485 would appear to be an evolved star lying close to or on the horizontal branch.

A Be star with a low nitrogen abundance in the SMC cluster NGC330

High- resolution UVES/ VLT spectra of B 12, an extreme pole- on Be star in the SMC cluster NGC 330, have been analysed using non-LTE model atmospheres to obtain its chemical composition relative to the SMC standard star AV304. We find a general underabundance of metals which can be understood in terms of an extra contribution to the stellar continuum due to emission from a disk which we estimate to be at the similar to 25% level. When this is corrected for, the nitrogen abundance for B12 shows no evidence of enhancement by rotational mixing as has been found in other non-Be B-type stars in NGC 330, and is inconsistent with evolutionary models which include the effects of rotational mixing. A second Be star, NGC330-B 17, is also shown to have no detectable nitrogen lines. Possible explanations for the lack of rotational mixing in these rapidly rotating stars are discussed, one promising solution being the possibility that magnetic fields might inhibit rotational mixing.

Detection of a Red Supergiant Progenitor Star of a Type II-Plateau Supernova

We present the discovery of a red supergiant star that exploded as supernova 2003gd in the nearby spiral galaxy M74. The Hubble Space Telescope (HST) and the Gemini Telescope imaged this galaxy 6 to 9 months before the supernova explosion, and subsequent HST images confirm the positional coincidence of the supernova with a single resolved star that is a red supergiant of 8+4-2 solar masses. This confirms both stellar evolution models and supernova theories predicting that cool red supergiants are the immediate progenitor stars of type II-plateau supernovae.

The massive binary companion star to the progenitor of supernova 1993J

The massive star that underwent a collapse of its core to produce supernova (SN)1993J was subsequently identified as a non-variable red supergiant star in images of the galaxy M81 taken before explosion(1, 2). It showed an excess in ultraviolet and B-band colours, suggesting either the presence of a hot, massive companion star or that it was embedded in an unresolved young stellar association1. The spectra of SN1993J underwent a remarkable transformation from the signature of a hydrogen-rich type II supernova to one of a helium-rich (hydrogen-deficient) type Ib(3, 4). The spectral and photometric peculiarities were best explained by models in which the 13�20 solar mass supergiant had lost almost its entire hydrogen envelope to a close binary companion(5, 6, 7), producing a 'type IIb' supernova, but the hypothetical massive companion stars for this class of supernovae have so far eluded discovery. Here we report photometric and spectroscopic observations of SN1993J ten years after the explosion. At the position of the fading supernova we detect the unambiguous signature of a massive star: the binary companion to the progenitor.

A search for star formation around the Galactic halo B-type star PHL 346 with the 2dF spectrograph

A preliminary search for stars that may have formed coevally with the apparently young halo B-type star PHL 346 has been performed with the 2dF multifibre spectrograph on the Anglo- Australian Telescope (AAT). Candidates were selected for spectroscopy from APM scans of B and R Schmidt plates centred on PHL 346. A total of 476 stars of spectral type A or F were found; radial velocity estimates and more accurate spectral type assignments narrowed the number of possible coeval candidates to 6 A-type and 14 F-type stars. A statistical analysis of these results using a comparison with a control field suggests that the number of A-type or F-type candidate stars around PHL 346 is not unexpected, and that they need not be associated with PHL 346. A number of ways to improve the project are suggested.