Competing kinetic pathways in the bromine addition to allylic ethers in 1,2‐dichloroethane: Opposite temperature effects

The kinetics of the electrophilic bromination of three allylic ethers in a nonprotic solvent, 1,2‐dichloroethane, has been investigated. Two of them followed a prevalent second‐order pathway, while the third one exhibited a classical, clean third order. The second‐order pathway in the first two olefins is attributed to electrophilic assistance of the ethereal oxygen to the attacking bromine molecule. In the molecular bromination of 2,4‐cis‐dimethyl‐8‐oxabicyclo[3.2.1]‐6‐octen‐3‐cis‐ol, opposite temperature dependences were found for the two different kinetic pathways. An exoergonic process for the second‐order reaction was explained by the lesser stability of the bromiranium–bromide ionic intermediate, compared to the bromiranium–tribromide in the third‐order profile. © 2007 Wiley Periodicals, Inc. 39: 197–203, 2007     

The effect of the anion on the physical properties of trihalide-based N,N-dialkylimidazolium ionic liquids

Low viscosity, high density trihalide-based 1-n-butyl-3-methylimidazolium ionic liquids have been prepared and characterised. Key physical properties (density, conductivity, melting point, refractive index, surface tension and diffusion coefficient) of the ionic liquids have been determined and are compared with those of other 1,3-dialkylimidazolium molten salts. The relationship between anion identity and the physical properties of the ionic liquids under investigation is discussed.     

Polarizability effects and dispersion interactions in alkene-Br2 pi-complexes

Weakly bound molecular complexes play an important role in chemistry, physics, and biodisciplines. The preequilibrium pi-complexes of various alkenes with bromine have been examined quantitatively, and a direct relationship between association constants (KF) of these pi-complexes and polarizability of the olefins was found. The stability of the Br2-olefin pi complexes is affected by both the donor ionization potential and the polarizability of the olefin, and an equation able to take into account both effects is proposed.     

Enhancement of persistent currents due to confinement in metallic samples

Confinement and surface roughness (SR) effects on the magnitude of the persistent current are analyzed for ballistic bidimensional metallic samples. Depending on the particular geometry, localized border states can show up at half-filling. These border states contribute coherently to the persistent current and its magnitude is enhanced with respect to their value in the absence of confinement. A linear scaling of the typical current I(typ) with the number of conduction channels M is obtained. This result is robust with respect to changes in the relevant lengths of the samples and to the SR. Possible links of our results to experiments are also discussed.     

Currents along ring arms with quantum dots: Kondo and Aharonov–Bohm effects

Transport properties of a double-dot system in a ring structure threaded by a magnetic flux are studied. The Aharonov–Bohm effect combined with the charging effects of the dots in the Kondo regime determines the phases of the currents going through each arm of the ring. Depending upon the magnetic flux and the state of charge of the dots, controlled by gate potentials, current circulates around the ring.     

Singlet-triplet transition in a quantum dot: effect on mesoscopic transport

The T=0 transport properties of a wire interacting with a lateral two-level quantum dot are studied by using an exact numerical calculation. The wire conductance, the spin–spin correlation and the Kondo temperature are obtained as a function of the dot level energy spacing. When the dot has two electrons and spin S_D1, the wire current is totally quenched by the S=1 Kondo effect. The Kondo temperature is maximum at the singlet–triplet transition and its dependence upon the dot energy spacing follows a non-universal scaling law.     

Spin structure of surface-supported single-molecule magnets from isomorphous replacement and X-ray magnetic circular dichroism

Surface-supported arrays of Fe(4)-type Single-Molecule Magnets retain a memory effect and are of current interest in the frame of molecule-based information storage and spintronics. To reveal the spin structure of [Fe(4)(L)(2)(dpm)(6)] (1) on Au, an isomorphous compound [Fe(3)Cr(L)(2)(dpm)(6)] was synthesized and structurally and magnetically characterized (H(3)L is tripodal ligand 11-(acetylthio)-2,2-bis(hydroxymethyl)undecan-1-ol and Hdpm is dipivaloylmethane). The new complex contains a central Cr(3+) ion and has a S = 6 ground state as opposed to S = 5 in 1. Low-temperature X-ray Magnetic Circular Dichroism studies at Fe- and Cr-L(2,3) edges revealed that the antiparallel alignment between Fe and Cr spins is preserved on surfaces. Moreover, the different Fe-L(2,3) spectral features found in the homo- and heterometallic species disclose the opposing contribution of the central Fe(3+) ion in the former compound, proving that its ferrimagnetic spin structure is retained on surfaces.