Room Temperature Ionic Liquids in Asymmetric Hetero-Ene Type Reactions: Improving Organocatalyst Performance at Lower Temperatures

Room temperature ionic liquids (RTILs) have been widely used as (co)solvents in several catalytic processes modifying, in most of the cases, the catalyst activity and/or the selectivity for the studied reactions. However, there are just a few examples of their use in hydrogen bonding organocatalysis. In this paper, we show the positive effect of a set of imidazole-based ionic liquids ([bmim]BF₄ and [hmim]PF₆) in the enantioselective addition of formaldehyde tert-butylhydrazone to prochiral α-keto esters catalyzed by a sugar-based chiral thiourea. Reactions performed in the presence of low percentages of RTILs led to an increase of the catalyst activity, thereby making possible to work at lower temperatures. Thus, the chiral tert-butyl azomethyl tertiary alcohols could be obtained with moderate to good conversions and higher enantioselectivities for most of the studied substrates when using up to 30 vol% of [hmim]PF₆ as a cosolvent in processes performed in toluene.     

Pressure-induced two-color photoluminescence in MnF(2) at room temperature

A novel two-color photoluminescence (PL) is found in MnF(2) at room temperature under high pressure. Contrary to low-temperature PL, PL at room temperature is unusual in transition-metal concentrated materials like MnF(2), since the deexcitation process at room temperature is fully governed by energy transfer to nonradiative centers. We show that room-temperature PL in MnF(2) originates from two distinct Mn(2+) emissions in the high-pressure cotunnite phase. The electronic structure and the excited-state dynamics are investigated by time-resolved emission and excitation spectroscopy at high pressure.     

Oscillatory persistent currents in self-assembled quantum rings

We report the direct measurement of the persistent current carried by a single electron by means of magnetization experiments on self-assembled InAs/GaAs quantum rings. We measured the first Aharonov-Bohm oscillation at a field of 14 T, in perfect agreement with our model based on the structural properties determined by cross-sectional scanning tunneling microscopy measurements. The observed oscillation magnitude of the magnetic moment per electron is remarkably large for the topology of our nanostructures, which are singly connected and exhibit a pronounced shape asymmetry.     

Spectral-fluctuations test of the quark-model baryon spectrum

We study the low-lying baryon spectrum (up to 2.2 GeV) provided by experiments and different quark models using statistical tools which allow us to postulate the existence of missing levels in spectra. We confirm that the experimental spectrum is compatible with random matrix theory, the paradigmatic model of quantum chaos, and we find that the quark models are more similar to a Poisson distribution, which is not compatible with what should be expected in a correlated spectrum. From our analysis it stems that the spectral fluctuation properties of quark-model spectra are incompatible with experimental data. This result can be used to enlighten the problem of missing resonances.     

Fermion family recurrences in the Dyson–Schwinger formalism

We study the multiple solutions of the truncated propagator Dyson–Schwinger equation for a simple fermion theory with Yukawa coupling to a scalar field. Upon increasing the coupling constant g, other parameters being fixed, more than one non-perturbative solution breaking chiral symmetry becomes possible and we find these numerically. These “recurrences” appear as a mechanism to generate different fermion generations as quanta of the same fundamental field in an interacting field theory, without assuming any composite structure. The number of recurrences or flavors is reduced to the question of the value of the Yukawa coupling, and it has no special profound significance in the standard model. The resulting mass function can have one or more nodes and the measurement that potentially detects them can be thought of as a collider-based test of the virtual dispersion relation for the charged lepton member of each family. This requires the three independent measurements of the charged lepton’s energy, three-momentum and off-shellness. We illustrate how this can be achieved for the (more difficult) case of the tau lepton. PACS 12.15.Ff; 11.30.Rd     

Isotropic compensation of diffraction-driven angular dispersion

We report on an optical arrangement capable of compensating angular dispersion of paraxial wave fields developed by diffractive optical elements (DOEs). Schematically, the system is a beam expander in which two phase-only zone plates have been inserted, remaining afocal the coupled system. The DOE, which induces a continuous set of dispersive tilted plane waves, is placed at a specific position within the proposed setup providing an output spectrum with achromatic angular deviation. A directional matching between phase fronts and pulse fronts of output wave packets is demonstrated.     

Analytical and statistical studies of Rodriguez–Velazquez indices

Journal of Mathematical Chemistry - In this work we perform analytical and statistical studies of the Rodríguez–Velázquez (RV) indices on graphs G. The topological RV(G) indices,...     

Stability of AgIII towards Halides in Organosilver(III) Complexes

The involvement of silver in two-electron Ag^I/Ag^III processes is currently emerging. However, the range of stability of the required and uncommon Ag^III species is virtually unknown. Here, the stability of Ag^III towards the whole set of halide ligands in the organosilver(III) complex frame [(CF₃)₃AgX]⁻ (X=F, Cl, Br, I, At) is theoretically analyzed. The results obtained depend on a single factor: the nature of X. Even the softest and least electronegative halides (I and At) are found to form reasonably stable Ag^III−X bonds. Our estimates were confirmed by experiment. The whole series of nonradiative halide complexes [PPh₄][(CF₃)₃AgX] (X=F, Cl, Br, I) has been experimentally prepared and all its constituents have been isolated in pure form. The pseudohalides [PPh₄][(CF₃)₃AgCN] and [PPh₄][(CF₃)₃Ag(N₃)] have also been isolated, the latter being the first silver(III) azido complex. Except for the iodo compound, all the crystal and molecular structures have been established by single-crystal X-ray diffraction methods. The decomposition paths of the [(CF₃)₃AgX]⁻ entities at the unimolecular level have been examined in the gas phase by multistage mass spectrometry (MSⁿ). The experimental detection of the two series of mixed complexes [CF₃AgX]⁻ and [FAgX]⁻ arising from the corresponding parent species [(CF₃)₃AgX]⁻ demonstrate that the Ag−X bond is particularly robust. Our experimental observations are rationalized with the aid of theoretical methods. Smooth variation with the electronegativity of X is also observed in the thermolyses of bulk samples. The thermal stability in the solid state gradually decreases from X=F (145 °C, dec.) to X=I (78 °C, dec.) The experimentally established compatibility of Ag^III with the heaviest halides is of particular relevance to silver-mediated or silver-catalyzed processes.