Single-crystal neutron diffraction under high pressures: valence instabilities in Tm monochalcogenides

New high-pressure devices based on the use of sapphire anvils now allow single-crystal neutron diffraction experiments to be performed up to P=8–10 GPa. After giving a brief overview of the technique, we present its application to the study of pressure-induced valence instabilities in Tm monochalcogenides (TmX, X: S, Se, Te). A variety of new magnetic phases have been characterized, yielding a consistent picture of the evolution of magnetism through the series. The results indicate a striking interplay between magnetic order taking place at low temperature and different types of electronic ground states (classical semiconductor, narrow-gap Kondo insulator, metallic Kondo lattice, etc.) inferred from the transport properties. This revised version was published online in July 2006 with corrections to the Cover Date.     

Unexpected Coordination Behaviour of a Polypyrrole Ligand

The first coordination compounds of a hexapyrrin reveal an unexpected binding mode of longer open‐chain oligopyrroles to transition metal ions as observed by the X‐ray structural analysis of a Pd^II derivative.     

An Unusual Mixed‐Anionic Iodine‐Rich Polyiodide: [Rb(crypt‐2,2,2)]4(I5)2(I8)

Black crystals of [Rb(crypt‐2,2,2)]₄(I₅)₂(I₈) were obtained from a dichloromethane/ethanol solution of RbI, I₂ and Kryptofix‐2,2,2®. The crystal structure (monoclinic, P2₁/c (no. 14), a = 1250.1(1), b = 2555.2(2), c = 2313.4(3) pm, β = 121.45(1)°, V = 6309.9(11)·10⁶ pm³, Z = 2) consists of [Rb(crypt‐2,2,2)]⁺ cations leaving three‐dimensional channels for the V‐shaped (I₅)^? and Z‐shaped (I₈)^2? anions which are isolated from each other.     

Iron chelates of 2,2'-bidipyrrin: stable analogues of the labile iron bilins

A unique series of halogenidoiron(III) complexes of the open-chain tetrapyrrolic ligand 2,2'-bidipyrrin (bpd) ([FeX(bdp)] X=F, Cl, Br, I) was prepared from simple pyrrolic and bipyrrolic precursors and iron chloride by a one-pot condensation/metalation strategy, followed by salt metathesis with CsF, LiBr, or NaI. Crystallographic analysis revealed that in all cases the 2,2'-bidipyrrin ligand is forced to reside in a helical conformation when bound to the iron atom. Whereas the extremely sensitive fluorido derivative was isolated as a CsF adduct and forms 1D polymeric chains in the solid state, the more stable chlorido, bromido, and iodido derivatives crystallize as discrete monomeric molecules with a distorted pentacoordinate iron(III) ion in an intermediate spin ground state. Magnetic susceptibility measurements and M?ssbauer data of the compounds are in agreement with this interpretation. In solution, however, all the compounds are pentacoordinate with the iron atom in the high-spin (S=5/2) state and dynamic with respect to helix inversion. In the presence of air, the iron chelates react stepwise with the nucleophiles methanol and imidazolate at the tetrapyrrole terminal alpha,omega-positions, presumably through the hexacoordinate species [Fe(bdp)(MeOH)2]+ and [Fe(im)2-(bdp)](-), respectively. The successive increase of strain at these positions results in increasingly labile intermediates that spontaneously release the iron ion from the mono- or disubstituted tetrapyrrole ligands.     

Bis(BF2)-2,2'-bidipyrrins (BisBODIPYs): highly fluorescent BODIPY dimers with large stokes shifts

Four new dimeric bis(BF(2))-2,2'-bidipyrrins (bisBODIPYs), and their corresponding BODIPY monomers, have been prepared and studied with respect to their structural and photophysical properties. The solid-state molecular structure of the dimers and the relative orientation of the subunits have been revealed by an X-ray diffraction study, which showed that the molecules contain two directly linked BODIPY chromophores in a conformationally fixed, almost orthogonal arrangement. Two of the fluorine atoms are in close contact with each other and the (19)F NMR spectra show a characteristic through-space coupling in solution. The new chromophores all exhibit a clear exciton splitting in the absorption spectra with maxima at about 490 and 560 nm, and are highly luminescent with an intense emission band at around 640 nm. The Stokes shift, which is the difference between the maximum of the lowest-energy absorption band and the maximum of the emission band, has a typical value of 5 to 15 nm for simple BODIPYs, whereas this value increases to 80 nm or more for the dimers, along with a slight decrease in fluorescence quantum yields and lifetimes. These properties indicate potential uses of these new fluorophoric materials as functional dyes in biomedical and materials applications and also in model compounds for BODIPY aggregates.     

Growth of conjugacy classes of Schottky groups in higher rank symmetric spaces

Let X be a globally symmetric space of noncompact type and rank greater that one, and a Schottky group of axial isometries. Then is a locally symmetric Riemannian manifold of infinite volume. The goal of this note is to give an asymptotic estimate for the number of primitive closed geodesics in M modulo free homotopy with period less than t.     

Single molecule spectroscopy of conjugated polymer chains in an electric field-aligned liquid crystal

Using single molecule polarization spectroscopy, we investigated the alignment of a polymer solute with respect to the liquid crystal (LC) director in an LC device while applying an external electric field. The polymer solute is poly[2-methoxy-5-(2'-ethyl-hexyloxy)-1,4-phenylene vinylene] (or MEH-PPV), and the LC solvent is 5CB. The electric field induces a change in the LC director orientation from a planar alignment (no electric field) to a perpendicular (homeotropic) alignment with an applied field of 5.5 x 103 V/cm. We find that the polymer chains align with the LC director in both planar and homeotropic alignment when measured in the bulk of the LC solution away from the device interface. Single molecule polarization distributions measured as a function of distance from the LC device interface reveal a continuous change of the MEH-PPV alignment from planar to homeotropic. The observed polarization distributions are modeled using a conventional elastic model that predicts the depth profile of the LC director orientation for the applied electric field. The excellent agreement between experiment and simulations shows that the alignment of MEH-PPV follows the LC director throughout the LC sample. Furthermore, our results suggest that conjugated polymers such as MEH-PPV can be used as sensitive local probes to explore complex (and unknown) structures in anisotropic media.     

Pulsed electron nuclear double resonance studies of the photoexcited triplet state of pentacene in p-terphenyl crystals at room temperature

Pulsed electron nuclear double resonance (ENDOR) using a modified Davies-type [Phys. Lett. 47A, 1 (1974)] sequence is employed to study the hyperfine (HF) structure of the photoexcited triplet state of pentacene dispersed in protonated and deuterated p-terphenyl single crystals. The strong electron spin polarization and long phase memory time of triplet pentacene enable us to perform the ENDOR measurements on the S=1 spin system at room temperature. Proton HF tensor elements and spin density values of triplet pentacene are extracted from a detailed angular-dependent study in which the orientation of the magnetic field is varied systematically in two different pentacene planes. Analysis reveals that the pentacene molecule is no longer planar in the p-terphenyl host lattice. The distortion is more pronounced in the deuterated crystal where the unit cell dimensions are slightly smaller than those of the protonated crystal.     

Topological changes in bipolar nematic droplets under flow

Bipolar liquid crystal drops moving inside microchannels exhibit periodic director field transformations due to induced circulating flows inside them. These modifications are characterized by changes in the type of point surface disclinations; they periodically change from splay to bend disclinations, implying the drop changes between bipolar and escaped concentric configurations. Upon stopping the flow, this structure does not relax to the lower energy bipolar configuration; we argue this is due to drop flattening inside the channels.     

Evidence for heating of neutron stars by magnetic-field decay

We show the existence of a strong trend between neutron star (NS) surface temperature and the dipolar component of the magnetic field extending through three orders of field magnitude, a range that includes magnetars, radio-quiet isolated neutron stars, and many ordinary radio pulsars. We suggest that this trend can be explained by the decay of currents in the crust over a time scale of approximately 10(6) yr. We estimate the minimum temperature that a NS with a given magnetic field can reach in this interpretation.