Assembly of a trinuclear metallo-capsule from a tripodal tris(beta-diketone) derivative and copper(II)

A new metallo-capsule has been synthesised that consists of three copper(II) ions and two molecules of a tris-deprotonated tripodal ligand in which three 2,4-pentanedione groups are linked via their gamma-carbons through thioether spacers to the 1,3,5-positions of a triazine core.     

Time Flat Surfaces and the Monotonicity of the Spacetime Hawking Mass II

In this sequel paper, we give a shorter, second proof of the monotonicity of the Hawking mass for time flat surfaces under spacelike uniformly area expanding flows in spacetimes that satisfy the dominant energy condition. We also include a third proof which builds on a known formula and describe a class of sufficient conditions of divergence type for the monotonicity of the Hawking mass. These flows of surfaces may have connections to the problem in general relativity of bounding the total mass of a spacetime from below by the quasi-local mass of spacelike 2-surfaces in the spacetime.     

Selective ruthenium-catalyzed transformations of enynes with diazoalkanes into alkenylbicyclo[3.1.0]hexanes

Reaction of a variety of CCH bond-containing 1,6-enynes with N2CHSiMe3 in the presence of RuCl(COD)Cp* as catalyst precursor leads, at room temperature, to the general formation of alkenylbicyclo[3.1.0]hexanes with high Z-stereoselectivity of the alkenyl group and cis arrangement of the alkenyl group and an initial double-bond substituent, for an E-configuration of this double bond. The stereochemistry is established by determining the X-ray structures of three bicyclic products. The same reaction with 1,6-enynes bearing an R substituent on the C1 carbon of the triple bond results in either cyclopropanation of the double bond with bulky R groups (SiMe3, Ph) or formation of alkylidene-alkenyl five-membered heterocycles, resulting from a beta elimination process, with less bulky R groups (R = Me, CH2CH=CH2). The reaction can be applied to in situ desilylation in methanol and direct formation of vinylbicyclo[3.1.0]hexanes and to the formation of some alkenylbicyclo[4.1.0]heptanes from 1,7-enynes. The catalytic formation of alkenylbicyclo[3.1.0]hexanes also takes place with enynes and N2CHCO2Et or N2CHPh. The reaction can be understood to proceed by an initial [2+2] addition of the Ru=CHSiMe3 bond with the enyne CCH bond, successively leading to an alkenylruthenium-carbene and a key alkenyl bicyclic ruthenacyclobutane, which promotes the cyclopropanation, rather than metathesis, into bicyclo[3.1.0]hexanes. Density functional theory calculations performed starting from the model system Ru(HCCH)(CH2=CH2)Cl(C5H5) show that the transformation into a ruthenacyclobutane intermediate occurs with a temporary eta3-coordination of the cyclopentadienyl ligand. This step is followed by coordination of the alkenyl group, which leads to a mixed alkyl-allyl ligand. Because of the non-equivalence of the terminal allylic carbon atoms, their coupling favors cyclopropanation rather than the expected metathesis process. A direct comparison of the energy profiles with respect to those involving the Grubbs catalyst is presented, showing that cyclopropanation is favored with respect to enyne metathesis.     

Unilateral MRI using a rastered projection

Unilateral magnetic resonance techniques, where magnet and radio frequency (RF) coil are placed on one side of the sample, can provide valuable information about a sample which otherwise cannot be accommodated in conventional high spectral resolution magnetic resonance systems. A unilateral magnetic resonance imaging approach utilizing the stray field from a disc magnet and a butterfly geometry RF coil is described. The coil excites spins in a volume centered around an arc through the sample. Translating the RF coil relative to the magnet and recording the signal at each translational location creates a projection of the signal in a tomographic slice through the sample. Rotating the RF coil relative to the sample and repeating the translation creates projections through the sample at different angles. Backprojecting this information yields an image. A proof of concept device operating on this principle at 12.4 MHz was constructed and characterized. Projections through three phantoms are presented with a 1.2-4 cm field of view, thickness of 102 microm, and at a distance of 3mm from the RF coil and 14 mm from the magnet. The edge spread function (ESF) was measured resulting in a 4mm full width at half maximum (FWHM) line spread function (LSF) estimation using a Gaussian model. An example of one reconstructed image is presented.     

Sultones and Sultines via a Julia–Kocienski Reaction of Epoxides

The development of the homologous Julia–Kocienski reaction has led to the discovery of two new reaction modes of epoxides with sulfones. These pathways allow rapid and direct access to a range of γ‐sultones and γ‐sultines.     

High Pressure Spectroscopy of Ti Doped Al2O3 and YAIO3 Host Crystals

We report high-pressure luminescence spectroscopy studies of Ti^3? in Al₂O₃ and YAlO₃. High-pressure luminescence spectra were measured for Al₂O₃:Ti^3? up to 90kbar and for YAlO₃:Ti^3? up to 181 kbar. In both cases, a blue shift of the luminescence peak with pressure was observed and is attributed to an increase in the octahedral crystal-field strength (10 Dq) with pressure. In the case of YAlO₃;Ti^3?, an additional luminescence peak was observed at 181 kbar and below ～ 200 K, and is attributed to a metastable state. The metastability of the ²E excited state was induced by pressure that removes the equivalency of three energy minima of the ²E state coupled to the ? mode.     

Theory of phase-ordering kinetics

The theory of phase-ordering dynamics that is the growth of order through domain coarsening when a system is quenched from the homogeneous phase into a broken-symmetry phase, is reviewed, with the emphasis on recent developments. Interest will focus on the scaling regime that develops at long times after the quench. How can one determine the growth laws that describe the time dependence of characteristic length scales, and what can be said about the form of the associated scaling functions? Particular attention will be paid to systems described by more complicated order parameters than the simple scalars usually considered, for example vector and tensor fields. The latter are needed, for example, to describe phase ordering in nematic liquid crystals, on which there have been a number of recent experiments. The study of topological defects (domain walls, vortices, strings and monopoles) provides a unifying framework for discussing coarsening in these different systems.     

Compression of antiproton clouds for antihydrogen trapping

Control of the radial profile of trapped antiproton clouds is critical to trapping antihydrogen. We report the first detailed measurements of the radial manipulation of antiproton clouds, including areal density compressions by factors as large as ten, by manipulating spatially overlapped electron plasmas. We show detailed measurements of the near-axis antiproton radial profile and its relation to that of the electron plasma.     

The relative performance of the local density approximation and gradient-corrected density functional theory for computing metal–ligand distances in Werner-type and organometallic complexes

Optimized metal-ligand (M-L) bond lengths for 17 classical Werner-type transition-metal complexes were calculated using the local density approximation (LDA) and a gradient-corrected (GC) extension. GCs lengthen the bonds by between 0.02 and 0.09 Å relative to the LDA results. The latter range from 0.02 Å shorter than observed to 0.05 Å longer, while the GC data range from exact agreement with experiment to some 0.12 Å too long. The LDA rms deviation is 0.025 Å compared to the GC error of 0.070 Å. In contrast, data from the literature for organometallic species show that the LDA gives systematically too short M-L distances and GCs lead to a better agreement with experiment. The relative performance of LDA and GC functionals reflects the qualitatively different chemistries of organometallic and Werner-type complexes. The magnitude of the GC bond-length expansion for the latter correlates with the ionicity of the M-L interaction. © 1997 John Wiley & Sons, Inc.