The role that minor mergers have played in the formation and structure of the Milky Way is still an open question, about which there is much debate. We use numerical simulations to explore the evolution of debris from a tidally disrupted satellite, with the aim of developing a method that can be used to identify and quantify signatures of accretion in a survey of halo stars. For a Milky Way with a spherical halo, we find that debris from minor mergers can remain aligned along great circles throughout the lifetime of the Galaxy. We exploit this result to develop the method of Great Circle Cell Counts (GC3), which we test by applying it to artificially constructed halo distributions. Our results suggest that if as few as 1\% of the stars in a halo survey are accreted from the disruption of a single subsystem smaller than the Large Magellanic Cloud, GC3 can recover the great circle associated with this debris. The dispersion in GC3 can also be used to detect the presence of structure characteristic of accretion in distributions containing a much smaller percentage of material accreted from any single satellite.Comment: 26 pages, AAS TeX, including 11 postscript figures. Accepted for publication in the Astrophysical Journal (Vol 466

The first enantioselective Brønsted acid catalyzed reduction of imines has been developed. This new organocatalytic transfer hydrogenation of ketimines with Hantzsch dihydropyridine as the hydrogen source offers a mild method to various chiral amines with high enantioselectivity. The stereochemistry of the chiral amines can be rationalized by a stereochemical model derived from an X-ray crystal structure of a chiral BINOL phosphate catalyst. [reaction: see text]

Selenolate is considered as an alternative to thiolate to serve as a headgroup mediating the formation of self-assembled monolayers (SAMs) on coinage metal substrates. There are, however, ongoing vivid discussions regarding the advantages and disadvantages of these anchor groups, regarding, in particular, the energetics of the headgroup-substrate interface and their efficiency in terms of charge transport/transfer. Here we introduce a well-defined model system of 6-cyanonaphthalene-2-thiolate and -selenolate SAMs on Au(111) to resolve these controversies. The exact structural arrangements in both types of SAMs are somewhat different, suggesting a better SAM-building ability in the case of selenolates. At the same time, both types of SAMs have similar packing densities and molecular orientations. This permitted reliable competitive exchange and ion-beam-induced desorption experiments which provided unequivocal evidence for a stronger bonding of selenolates to the substrate as compared to the thiolates. Regardless of this difference, the dynamic charge transfer properties of the thiolate- and selenolate-based adsorbates were found to be nearly identical, as determined by the core-hole-clock approach, which is explained by a redistribution of electron density along the molecular framework, compensating the difference in the substrate-headgroup bond strength.

The hydrogen-bridged disilyl cation 6 with an 1,8-naphthalenediyl backbone was synthesized and was characterized by NMR spectroscopy and X-ray crystallography, supported by quantum mechanical computations. The SiHSi linkage is symmetrical, corresponding to a single minimum potential, and the structural parameters are in agreement with the presence of a two electron-three center bond in 6. Treatment of disilyl cation 6 with alkyl fluorides yields the disilylfluoronium ion 10. The SiFSi group in the disilyl fluoronium ion 10 is symmetrical with an average SiF bond length of 175.9(8) and a bent angle beta = 130 degrees . Both cations catalyze the hydrodefluorination reaction of alkyl and benzyl fluorides to give alkanes.

Herein we show that replacing the two meso carbon atoms of the polycyclic aromatic hydrocarbon (PAH) bisanthene by boron atoms transforms a near-infrared dye into an efficient blue luminophore. This observation impressively illustrates the impact of boron doping on the frontier orbitals of PAHs. To take full advantage of this tool for the targeted design of organic electronic materials, the underlying structure-property relationships need to be further elucidated. We therefore developed a modular synthesis sequence based on a Peterson olefination, a stilbene-type photocyclization, and an Si-B exchange reaction to substantially broaden the palette of accessible polycyclic aromatic organoboranes and to permit a direct comparison with their PAH congeners.

9,10-Dihydro-9,10-diboraanthracene (DBA) provides a versatile scaffold for the development of boron-doped organic luminophores. Symmetrically C-halogenated DBAs are obtained through the condensation of 4-bromo-1,2-bis(trimethylsilyl)benzene or 4,5-dichloro-1,2-bis(trimethylsilyl)benzene with BBr3 in hexane. Unsymmetrically C-halogenated DBAs are formed via an electrophilic solvent activation reaction if the synthesis is carried out in o-xylene. Mechanistic insight has been achieved by in situ NMR spectroscopy, which revealed C-halogenated 1,2-bis(dibromoboryl)benzenes to be the key intermediates. Treatment of the primary 9,10-dibromo-DBAs with MesMgBr yields air- and water-stable C-halogenated 9,10-dimesityl-DBAs (2-Br-6,7-Me2-DBA(Mes)2; 2,6-Br2-DBA(Mes)2; 2,3-Cl2-6,7-Me2-DBA(Mes)2; 2,3,6,7-Cl4-DBA(Mes)2). Subsequent Stille-type C-C-coupling reactions give access to corresponding phenyl, 2-thienyl, and p-N,N-diphenylaminophenyl derivatives, which act as highly emissive donor-acceptor dyads or donor-acceptor-donor triads both in solution and in the solid state. 2-Thienyl was chosen as a model substituent to show that already a variation of the number and/or the positional distribution of the donor groups suffices to tune the emission wavelength of the resulting benchtop stable compounds from 469 nm (blue) to 540 nm (green). A further shift of the fluorescence maximum to 594 nm (red) can be achieved by switching from 2-thienyl to p-aminophenyl groups. A comparison of the optoelectronic properties of selected C-substituted DBA(Mes)2 derivatives with those of the isostructural anthracene analogues unveiled the following: (i) The DBA core is a much better electron acceptor. (ii) The emission colors of DBAs fall in the visible range of the spectrum (blue to orange), while anthracenes emit exclusively in the near-ultraviolet to blue wavelength regime. (iii) DBAs show significantly higher solid-state quantum yields.

Iron chains: The highly soluble, ferrocene‐containing polymer [‐fc‐B(Mes)‐]n (fc=Fe(C5H4)2, Mes=mesityl), with an average chain length of about 16 repeat units (n=16), is readily accessible by a novel polycondensation reaction starting from fc(BBr2)2 and HSiEt3 (see scheme). The polymer contains three‐coordinate boron centers, which are well‐suited for the promotion of electron delocalization along the polymer chain.

Building bridges: The title compound forms an unprecedented polymeric structure with bridging B-H-B three-center two-electron bonds in the solid state. This organoborane serves as an efficient precursor for the preparation of boron-doped pi-conjugated polymers by hydroboration polymerization with a functionalized 1,4-diethynylbenzene (see picture). These polymers form thin films that show intense green luminescence.