Anharmonic Computations Meet Experiments (IR, Raman, Neutron Diffraction) for Explaining the Behavior of 1,3,5-Tribromo-2,4,6-trimethylbenzene.

In the present paper we first show the experimental Raman, infrared, and neutron INS spectra of tribromomesitylene (TBM) measured in the range 50-3200 cm(-1) using crystalline powders at 6 or 4 K. Then, the bond lengths and angles determined by neutron diffraction using a TBM single crystal at 14 K are compared to the computed ones at different levels of theory. Anharmonic computations were then performed on the relaxed structure using the VPT2 approach, and for the lowest normal modes, the HRAO model has led to a remarkable agreement for the assignment of the experimental signatures.

Phosphinocyclodextrins as confining units for catalytic metal centres. Applications to carbon-carbon bond forming reactions.

The capacity of two cavity-shaped ligands, HUGPHOS-1 and HUGPHOS-2, to generate exclusively singly phosphorus-ligated complexes, in which the cyclodextrin cavity tightly wraps around the metal centre, was explored with a number of late transition metal cations. Both cyclodextrin-derived ligands were assessed in palladium-catalysed Mizoroki-Heck coupling reactions between aryl bromides and styrene on one hand, and the rhodium-catalysed asymmetric hydroformylation of styrene on the other hand. The inability of both chiral ligands to form standard bis(phosphine) complexes under catalytic conditions was established by high-pressure NMR studies and shown to have a deep impact on the two carbon-carbon bond forming reactions both in terms of activity and selectivity.

Cross-metathesis/isomerization/allylboration sequence for a diastereoselective synthesis of anti-homoallylic alcohols from allylbenzene derivatives and aldehydes.

We describe a highly diastereoselective approach to anti-homoallylic alcohols from allylbenzene derivatives and aldehydes. The strategy is based on a cross-metathesis/isomerization/allylboration sequence catalyzed successively by ruthenium and iridium. This methodology provides another way to access this class of compounds, which leads to the preparation of hitherto-unknown homoallylic alcohols without the requirement to control the stereochemistry of the 1-alkenyl boronate intermediates.

A novel, efficient synthesis of N-aryl pyrroles via reaction of 1-boronodienes with arylnitroso compounds.

A one-pot hetero-Diels-Alder/ring contraction cascade is presented from the reaction of 1-boronodienes and arylnitroso derivatives to derive N-arylpyrroles in moderate to good yields (up to 82%).

Tandem reactions involving 1-silyl-3-boryl-2-alkenes. New access to (Z)-1-fluoro-1-alkenes, allyl fluorides, and diversely α-substituted allylboronates.

The reactions of 1-silyl-3-boryl-2-alkenes with various electrophilic reagents (Selectfluor, N-halosuccinimides, benzhydryl, and propargylic alcohols in the presence of a Lewis acid, N-alkoxycarbonyliminium ion) have been investigated as new routes to α-substituted allylboronates. Further functional transformations, including allylboration, Suzuki coupling, protodeboronation, and cycloisomerization, have been carried out to illustrate the synthetic potential of these γ-borylallylsilanes.

Impact of a projectile on a granular medium described by a collision model.

We propose a model for the propagation of energy due to the impact of a granular projectile on a dense granular medium. Energy is transferred from grain to grain during binary collision events. The transport of energy may then be viewed as a random walk with a split of energy during successive collisions.

Orientation fields of nonlinear biological fibrils by second harmonic generation microscopy.

The orientation of fibrils within biological tissues is of primary importance. In this study, we propose a simple method based on second harmonic generation (SHG) microscopy to map, pixel by pixel, the orientation of the symmetry axis of the second-order nonlinear susceptibility tensor of fibrils that produce SHG. The method uses only four images acquired at specific polarizations of the input laser beam, and can be easily and cheaply implemented on a confocal microscope.

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.

On the existence of stationary states during granular compaction.

When submitted to gentle mechanical taps a granular packing slowly compacts until it reaches a stationary state that depends on the tap characteristics. The properties of such stationary states are experimentally investigated. The influence of the initial state, taps properties and tapping protocol are studied.

Density inversion in rapid granular flows: the supported regime.

This paper presents numerical findings on rapid 2D and 3D granular flows on a bumpy base. In the supported regime studied here, a strongly sheared, dilute and agitated layer spontaneously appears at the base of the flow and supports a compact packing of grains moving as a whole. In this regime, the flow behaves like a sliding block on the bumpy base.

Molecular dynamics of a short-range ordered smectic phase nanoconfined in porous silicon.

4-n-octyl-4-cyanobiphenyl has been recently shown to display an unusual sequence of phases when confined into porous silicon (PSi). The gradual increase of oriented short-range smectic (SRS) correlations in place of a phase transition has been interpreted as a consequence of the anisotropic quenched disorder induced by confinement in PSi. Combining two quasielastic neutron scattering experiments with complementary energy resolutions, the authors present the first investigation of the individual molecular dynamics of this system.

Pressure-induced lock-in in an aperiodic nanoporous crystal.

This Letter reports on the first observation of a commensurate lock-in inside an aperiodic composite. This result is obtained by neutron diffraction, under hydrostatic pressure, in the prototype self-assembled crystal of hexadecane urea. A selective compressibility of the sublattices is a required condition together with the existence of a lock-in energy term in these supramolecular materials.

Evidence of anisotropic quenched disorder effects on a smectic liquid crystal confined in porous silicon.

We present a neutron scattering analysis of the structure of the smectic liquid crystal octylcyanobiphenyl (8CB) confined in one-dimensional nanopores of porous silicon films (PS). The smectic transition is completely suppressed, leading to the extension of a short-range ordered smectic phase aligned along the pore axis. It evolves reversibly over an extended temperature range, down to 50 K below the N-SmA transition in pure 8CB.

Lanthanide complexes for second order nonlinear optics: evidence for the direct contribution of f electrons to the quadratic hyperpolarizability.

This study descibes for the first time the nonlinear optical (NLO) properties of multipolar lanthanide complexes, Na3[Ln(dipic)3]. The "metal-induced" NLO activity enhancement is confirmed as a general property of f-block elements, and the direct participation of f electrons to the hyperpolarizability beta is strongly supported by experimental data.

Experimental compaction of anisotropic granular media.

We report on experiments to measure the temporal and spatial evolution of packing arrangements of anisotropic and weakly confined granular material, using high-resolution gamma-ray adsorption. In these experiments, the particle configurations start from an initially disordered, low-packing-fraction state and under vertical solicitations evolve to a dense state. We find that the packing fraction evolution is slowed by the grain anisotropy but, as for spherically shaped grains, can be well fitted by a stretched exponential.

Importance of convection in the compaction mechanisms of anisotropic granular media.

We report the experimental observation of vortex patterns in a vertically tapped granular media. Depending on the tapping acceleration, two behaviors are observed. For high acceleration a convection vortex appears in the whole media, whereas for low acceleration two unstable vortices appear in the upper part of the media and slowly compact the lower part.

Organization and orientation of amphiphilic push-pull chromophores deposited in Langmuir-Blodgett monolayers studied by second harmonic generation and atomic force microscopy.

Orientation and organization of two amphiphilic push-pull chromophores mixed with two phospholipids (dipalmitoylphosphatidylcholine and dioleoylphosphatidylcholine) in Langmuir-Blodgett (LB) monolayers are investigated by second harmonic generation. The LB monolayers have also been characterized by atomic force microscopy and UV-vis spectroscopy. The effective molecular orientations and hyperpolarizabilities of the chromophores are studied as a function of the phospholipid concentrations.

Interactions in self-organized nanoporous organic crystals.

This Letter reports on the structural analysis of a self-assembly material, the prototype host-guest urea-alkane nanoporous crystal. Different spectroscopic techniques, under hydrostatic pressure, reveal a totally unexpected ordered phase where ordering does not require any apparent deformation of the host. This fundamental observation raises the question of the actual interactions in other similar supramolecular or biological tubular systems.

Structure of liquid and glassy methanol confined in cylindrical pores.

We present a neutron scattering analysis of the density and the static structure factor of confined methanol at various temperatures. Confinement is performed in the cylindrical pores of MCM-41 silicates with pore diameters D=24 and 35 A. A change of the thermal expansivity of confined methanol at low temperature is the signature of a glass transition, which occurs at higher temperature for the smallest pore.

First one-dimensional stress-strain experiments inside an aperiodic inclusion compound: evidence of depinning effects.

This Letter reports on the first observation of depinning under hydrostatic pressure of the guest and host sublattices inside the aperiodic nonadecane-urea inclusion compound. This leads to a unique way for a direct determination of the one-dimensional interguest interaction (1 N/m for nonadecane).

Selective Activation of Ar-Cl and Ar-C Bonds with Iron(II) Complexes.

The electrophilic iron-carbene chelate complexes 1 and 2 react with alkoxides RO to give the neutral chelate complex 3 and the carbene complex 4, respectively. Depending on the nature of the chelating ortho substituent, selective activation of the Ar-Cl or Ar-C bond occurs; these processes are promoted by the chelation.