Negatively Charged Metallacarborane Redox Couples with Both Members Stable to Air

The metallacarborane [3,3′‐Co(1,2‐closo‐C₂B₉H₁₁)₂]^? has been synthesized. This species allows the formation of redox couples in which both partners are negatively charged. The E_1/2 potential can be tuned by adjusting the nature and number of substituents on B and C. The octaiodinated species [3,3′‐Co(1,2‐closo‐C₂B₉H₇I₄)₂]^? is the most favorable, as it is isolatable and stable in air. A DFT study on stability and redox potentials of complexes has been performed.     

Summing the derivative expansion of the effective action

The derivative expansion of the effective action is a perturbative development in derivatives of the fields. The expansion breaks down when some of the derivatives are too large. We show how to sum exactly the first and second derivatives and treat perturbatively derivatives higher than second.     

Monte Carlo Simulation of Electron Transport and X-Ray Generation. II. Radiative Processes and Examples in Electron Probe Microanalysis

Theoretical models for Monte Carlo simulation of radiative processes, i.e. bremsstrahlung and characteristic x-ray emission, are presented. Possible strategies for simulating electron transport are briefly described. For mechanisms involving energy loss and angular deflections, difficulties for strict implementation of accurate numerical differential cross sections still remain due to the strong correlations between these variables. Practical solutions for the case of inelastic collisions and bremsstrahlung emission are described. Comparisons of simulation results with experimental data for several problems of interest in electron probe microanalysis are presented.     

Electrochemistry nanometric patterning of MOF particles: Anisotropic metal electrodeposition in Cu/MOF

Electrodeposition of copper from Cu/MOF immersed into acetate buffer produces a quasi-periodic series of 10–20 nm sized laminae sandwiched within the pristine MOF lattice as monitored by voltammetry of microparticles/atomic force microscopy. This anisotropic patterning can be qualitatively described in terms of a highly orientation-dependent diffusion of electrons and charge-balancing electrolyte counterions in the MOF network.     

Gold ultra-microelectrode arrays: application to the steady-state voltammetry of hydroxide ion in aqueous solution.

Gold ultra-microelectrode arrays are used to explore the electrochemical oxidation of hydroxide ions and are shown to be analytical useful. Two types of ultra-microelectrode arrays are used; the first consist of 256 individual electrodes of 5 microm in radius, 170 of which are electrochemically active in a cubic arrangement which are separated from their nearest neighbour by a distance of 100 microm. The second array compromises 2597 electrodes of 2.5 microm in radius and of which 1550 of which are electrochemically active in a hexagonal arrangement separated by the nearest neighbour by 55 microm. Well defined voltammetric waves are found with peak currents proportional to the concentration of hydroxide ions in the range 50 microM to 1 mM. Detection limits of 20 microM using the 170 ultra-microelectrode and 10 microM with the 1550 ultra-microelectrode array are shown to be possible but with a higher sensitivity of 4 mA M(-1) observed using the 1550 ultra-microelectrode array compared to 1.2 mA M(-1) with the 170 ultra-microelectrode array.     

A note on the acyclicity of the Koszul complex of a module

We prove the vanishing of the Koszul homology group H _μ(Kos(M)_μ), where μ is the minimal number of generators of M. We give a counterexample that the Koszul complex of a module is not always acyclic and show its relationship with the homology of commutative rings.     

Ferromagnetic coupling through spin polarization in the hexanuclear [MnII(3)CuII(3)] complex

A novel Cu(II)-Mn(II) hexanuclear complex of formula [[MnCuL](3)(tma)](ClO(4))(3).8H(2)O [H(2)L = macrocyclic Robson proligand; H(3)tma = trimesic acid] has been obtained by connecting three heterobinuclear [Cu(II)Mn(II)L](2+) cationic species through the trimesate anion. The complex exhibits a C(3) rotational symmetry, imposed by the geometry of the bridging ligand. The interaction within each Mn(II)-Cu(II) pair is antiferromagnetic (J = -16.7 cm(-1)). A weak ferromagnetic coupling among the three S = 2 resulting spins through the tricarboxylato bridge leads to a S = 6 ground spin state, for which the spin polarization mechanism is responsible.     

The modulating possibilities of dicarbollide clusters: optimizing the Kharasch catalysts

exo-Cluster dicarbollides substitution has allowed tuning of the E degrees (Ru(II)/Ru(III)) potential to obtain the best-performing Kharasch catalyst. We postulate that this is possible through the to-and-fro electron movement between the boron cluster and the sulfonium moieties.     

Aldol condensations over reconstructed Mg-Al hydrotalcites: structure-activity relationships related to the rehydration method

Two different rehydration procedures in the liquid or gas phase have been applied to reconstruct mixed oxides derived from calcined hydrotalcite-like materials to be used as catalysts for aldol condensation reactions. The as-synthesized hydrotalcite, its decomposition product, as well as the reconstructed solids upon rehydration were characterized by XRD, N(2) adsorption, He pycnometry, FTIR, SEM, TEM, (27)Al MAS-NMR and CO(2)-TPD (TPD=temperature-programmed desorption). Compared to the Mg-Al mixed oxide rehydrated in the gas phase (HT-rg), that rehydrated in the liquid phase (HT-rl) exhibits a superior catalytic performance with respect to the aldol condensation of citral with ketones to yield pseudoionones and in the self-aldolization of acetone. The textural properties of HT-rl and HT-rg differ strongly and determine the catalytic behavior. A memory effect led to a higher degree of reconstruction of the lamellar structure when the mixed oxide was rehydrated in the gas phase rather than in the liquid phase, although liquid-phase rehydration under fast stirring produced a surface area that was 26 times greater. This contrasts to typical statements in the literature claiming a higher degree of reconstruction in the presence of large amounts of water in the medium. CO(2)-TPD shows that the number of OH(-) groups and their nature are very similar in HT-rg and HT-rl, and cannot explain the markedly different catalytic behavior. Accordingly, only a small fraction of the available basic sites in the rehydrated samples is active in liquid-phase aldol condensations. Our results support the model in which only basic sites near the edges of the hydrotalcite platelets are partaking in aldol reactions. Based on this, reconstructed materials with small crystallites (produced by exfoliation during mechanical stirring), that is, possessing a high external surface area, are beneficial in the reactions compared to larger crystals with a high degree of intraplatelet porosity.