Rare azido-bridged manganese(II) systems: syntheses, crystal structures, and magnetic properties

Two new polymeric azido-bridged manganese complexes of formulas [Mn(N3)2 (bpee)]n (1) and {[Mn(N3)(dpyo)Cl(H2O)2](H2O)}n (2) [bpee, trans-1,2-bis(4-pyridyl)ethylene; dpyo, 4,4'-dipyridyl N,N'-dioxide] have been synthesized and characterized by single-crystal X-ray diffraction analysis and low-temperature magnetic study. Both the complexes 1 and 2 crystallize in the triclinic system, space group P1, with a = 8.877(3) A, b = 11.036(3) A, c = 11.584(4) A, alpha = 72.62(2) degrees, beta = 71.06(2) degrees, gamma = 87.98(3) degrees, and Z = 1 and a = 7.060(3) A, b = 10.345(3) A, c = 11.697(4) A, alpha = 106.86(2) degrees, beta = 113.33(2) degrees, gamma = 96.39(3) degrees, and Z = 2, respectively. Complex 1 exhibits a 2D structure of [-Mn(N3)2-]n chains, connected by bpee ligands, whose pyridine rings undergo pi-pi and C-H...pi interactions. This facilitates the rare arrangement of doubly bridged azide ligands with one end-on and two end-to-end (EO-EE-EE) sequence. Complex 2 is a neutral 1D polymer built up by [Mn(N3)(dpyo)Cl(H2O)2] units and lattice water molecules. The metals are connected by single EE azide ligands, which are arranged in a cis position to the Mn(II) center. The 1D zipped chains are linked by H-bonds involving lattice water molecules and show pi-pi stacking of dpyo pyridine rings to form a supramolecular 2D layered structure. The magnetic studies were performed in 2-300 K temperature range, and the data were fitted by considering an alternating chain of exchange interactions with S = 5/2 (considered as classical spin) with the spin Hamiltonians H = -Ji sigma(S(3i)S(3i+1) + S(3i+1)S(3i+2)) - J2 sigmaS(3i-1)S(3i) and H = -Ji sigmaS(2i)S(2i+1) - J2 sigmaS(2i+1)S(2i+2) for complexes 1 and 2, respectively. Complex 2 exhibits small antiferromagnetic coupling between the metal centers, whereas 1 exhibits a new case of topological ferromagnetism, which is very unusual.     

First-principles study of Ti-catalyzed hydrogen chemisorption on an Al surface: a critical first step for reversible hydrogen storage in NaAlH4

Complex metal hydrides are perhaps the most promising hydrogen storage materials for a gradual transformation to a hydrogen-based economy. We have used a computational approach to aid the ongoing experimental effort to understand the reversible hydrogen storage in Ti-doped NaAlH(4) and propose a plausible first step in the rehydrogenation mechanism. The study provides insight into the catalytic role played by the Ti atoms on an Al surface in the chemisorption of molecular hydrogen and identifies the local arrangement of the Ti atoms responsible for the process. Our results can potentially lead to ways of making other similar metal hydrides reversible.     

Thermally induced solid-state isomerisation and decomposition of 2,2-dimethyl-1,3-propanediamine nikel(II) complexes

Summary Complexes [NiL₃]Br₂·H₂O (L=2,2-dimethyl-1,3-propanediamine), [NiL₂X₂] (X=Cl, Br, NCS, CF₃CO₂, HCCl₂CO₂ or CCl₃CO₂ and X₂=SO₄ or SeO₄) and [NiL(HCCl₂CO₂)₂]·H₂O have been synthesised and their thermal studies have been investigated in the solid state. The complexes, [NiL₂X₂] (X=Cl or Br) and NiLX₂ (X=Cl or HCCl₂CO₂) have been isolated thermally in the solid state. All the complexes possess octahedral geometry. [NiL₂Br₂] and [NiL₂(CF₃CO₂)₂] exist in two interconvertible isomeric forms. H for the conversions were determined. [NiL₂(HCCl₂CO₂)₂] (5) undergoes an irreversible phase transition (178–188°C; H=4.4kJ mol^–1]. NiL(HCCl₂CO₂)₂·H₂O shows an exothermic irreversible phase transition (104–128°C; H=–5.8 kJ mol^–1) after losing water. The phase transitions are assumed to be due to the conformational changes in the chelate ring of diamine.     

From Structural Models of Galactose Oxidase to Homogeneous Catalysis: Efficient Aerobic Oxidation of Alcohols

Two reaction pathways are catalyzed by the dinuclear copper(II )–phenoxyl complex 1 —a functional model for the metalloenzyme galactose oxidase—by the oxidation of primary and secondary alcohols with dioxygen (air) in homogeneous solution to their corresponding aldehydes or ketones and/or 1,2-glycols (oxidative C–C coupling). The reduction product formed is H₂O₂, not water.     

Soft mode and related behaviour in the SmA and SmC* phases of a ferroelectric liquid crystalline polymer by dielectric spectroscopy

Anomalous dielectric relaxation behaviour is observed in the ferroelectric liquid crystalline polymer (viz. ferroelectric copolysiloxane (R)-COPS 11-10) around the ferroelectric SmC* to paraelectric SmA phase transition. Measurements have been performed on sample of thickness ～10 μm in indium-tin-oxide coated cell in the frequency range 10 Hz to 13 MHz. With increase of temperature, a gradual shift of the soft mode frequency towards the higher frequency side was observed, while a decrease in the relaxation strength was seen with the corresponding increase in temperature. The shifts of the soft modes in the SmC* and SmA phase are considered to be due to change in the viscosity of the polymer, as an increase in viscosity increases fluctuations of the coupling between the dipoles in the network even far from the paraelectric-ferroelectric phase transition. Application of a bias field causes a shift of the critical frequency towards the higher frequency side, while the dielectric strength (δε) decreases under the bias field. The Cole-Cole fitting parameters obtained from the best fit of the dielectric constant data are found to be consistent with other similar materials. Another relaxation mode (molecular mode) was also observed which comes into play in both the smectic phases (SmC% and SmA) and contributes to the dielectric permittivity.     

Tuning of spin transition in radical-containing iron(III) complexes by remote ligand substituents

Two new iron(III) complexes, Fe(III)(LF*)3 (1) and FeIII(L(t-Bu*))3 (2), of remote substituted o-aminophenol-based ligands are reported; complexes 1 and 2 contain three O,N-coordinated o-iminobenzosemiquinonate(1-) radical anions with ferric centers in high-spin and low-spin configurations. The crystal structures of 1 and 2 were determined by X-ray diffraction at 100 and 293 K, and the electronic structures were established by various physical methods including M?ssbauer (4-290 K) and variable-temperature (2-290 K) susceptibility measurements. Electrochemical measurements (cyclic and square-wave voltammetry) indicate primarily ligand-centered redox processes. Complex 1, with the more electron-withdrawing fluoro substituents, retains the high-spin character of the ferric ion throughout the temperature range studied (2-290 K) and exhibits, as expected, strong antiferromagnetic coupling operating between three radicals (SR = 1/2) and the high-spin Fe(III) center (SFe = 5/2) yielding an St = 1 as the ground state. In contrast, the occurrence of a thermally induced spin crossover process (SFe = 5/2 <--> SFe = 1/2) is observed for complex 2 FeIII(L(t-Bu*))3, in which more electron donating tert-butyl substituents in the ligand are present. A rationale for the control of the electronic state of ferric ions in 2 together with spin-coupling schemes for 1 and 2 are provided.     

Smoothed analysis of probabilistic roadmaps

The probabilistic roadmap algorithm is a leading heuristic for robot motion planning. It is extremely efficient in practice, yet its worst case convergence time is unbounded as a function of the input's combinatorial complexity. We prove a smoothed polynomial upper bound on the number of samples required to produce an accurate probabilistic roadmap, and thus on the running time of the algorithm, in an environment of simplices. This sheds light on its widespread empirical success.     

Communication: Universality of the melting curves for a wide range of interaction potentials

We demonstrate that the melting curves of various model systems of interacting particles collapse to (or are located very close to) a universal master curve on a plane of appropriately chosen scaled variables. The physics behind this universality is discussed. An equation for the emerging "universal melting curve" is proposed. The obtained results can be used to approximately predict melting of various substances in a wide range of conditions.     

A review of: “Advances in phase transitions”

From specific heat, thermal expansion, and dielectric constant measurements between 150 and 300 K we have confirmed the low temperature phase transition in barium chloride dihydrate (BaCl₂.2H₂O) at 195 ± 1 K. This transition appears to be associated with the local ordering (or displacements) of the two water molecules in the crystal. A “pseudospin” type model is proposed to explain the transition mechanism.     

An atomistic MD simulation and pair-distribution-function study of disorder and reactivity of alpha-AlF3 nanoparticles

Cubic nanoparticles of alpha-AlF(3) containing 864 and 2048 atoms were investigated by using molecular dynamics simulations. Significant structural rearrangements of these particles occurred, primarily at the edges and corners of the particles, and 3 and 5 membered (Al-F-)(n) ring structures were observed in addition to the 4-membered rings seen in bulk alpha-AlF(3). These 3 and 5 membered ring structures are, however, present in other metastable forms of AlF(3), which are formed at low temperatures from high surface area precursors. The surfaces of the nanoparticles were very dynamic on the timescale of the MD run, Al-F bonds being continually broken and formed, resulting in the movement of the low coordinate Lewis acid Al sites on the surfaces of the particles. The Lewis acid sites, which represent the catalytically active sites for F/Cl exchange reactions, are largely present at the corners and edges of the particles. The particles show larger rhombohedral distortions than present in the bulk phase and do not undergo a rhombohedral to cubic phase transition at elevated temperatures. The results are compared with pair distribution function (PDF) analysis results from fluorinated gamma-Al(2)O(3), nanoparticles of AlF(3) prepared by plasma routes and alpha- and beta-AlF(3). Broad peaks between 3.3 and 4.5 A in the PDF plots of the fluorinated Al(2)O(3) and the nanoparticles indicate a distribution of Al-F distances arising from Al and F atoms in connected AlF(6) octahedra; this is consistent with the presence of ring structures other than those found in alpha-AlF(3).