Structural and magnetic properties of the Kagomé antiferromagnet YbBaCo4O7

The mixed-valent compound YbBaCo₄O₇ is built up of Kagomé sheets of CoO₄ tetrahedra, linked in the third dimension by a triangular layer of CoO₄ tetrahedra in an analogous fashion to that found in the known geometrically frustrated magnets such as pyrochlores and SrCr_9xGa_12−9xO₁₉ (SCGO). We have undertaken a study of the structural and magnetic properties of this compound using combined high-resolution powder neutron and synchrotron X-ray diffraction. YbBaCo₄O₇ undergoes a first-order trigonal→orthorhombic phase transition at 175 K. We show that this transition occurs as a response to a markedly underbonded Ba²⁺ site in the high-temperature phase and does not appear to involve charge ordering of Co²⁺/Co³⁺ ions in the tetrahedra. The symmetry lowering relieves the geometric frustration of the structure, and a long-range-ordered 3-D antiferromagnetic state develops below 80 K.     

Potentiometric titration of permanganate with resacetophenone oxime

Milligram amounts of permanganate can be titrated with resacetophenone oxime (4-acetylresorcinol oxime) as a reducing titrant in the presence of phosphoric acid (0.5 M). The stoichiometry between permanganate and the oxime is 3:1 (MnO₄^-:oxime). The titration is successful in the presence of large amounts of dichromate or vanadate or moderate amounts of cerium(IV).     

Palladium(II) and platinum(II) complexes of Schiff bases derived from 2,6-diacetylpyridine and S-methyldithiocarbazate and the X-ray crystal structure of the [Pd(mdapsme)Cl] complex

Condensation of 2,6-diacetylpyridine (dap) with S-methyldithiocarbazate (smdtc) in a 1:2 molar ratio yields a bicondensed pentadentate Schiff base (H₂dapsme) which reacts with K₂MCl₄ (M = Pd^II, Pt^II) giving stable complexes of empirical formula, [M(dapsme)] · 0.5Me₂CO. These complexes have been characterized by a variety of physico-chemical techniques. Condensation of dap with smdtc in a 1:1 molar ratio also yields the bicondensed Schiff base (H₂dapsme) as the major product, but a mono-condensed one-armed Schiff base (Hmdapsme) is also obtained as a minor product. The latter reacts with K₂PdCl₄ in an EtOH–H₂O mixture yielding a crystalline complex of empirical formula, [Pd(mdapsme)Cl], the crystal structure of which has been determined by X-ray diffraction. The complex has a distorted square-planar structure in which the ligand is coordinated to the palladium(II) ion as a uninegatively charged tridentate chelating agent via the pyridine nitrogen atom, the azomethine nitrogen atom and the thiolate sulfur atom; the oxygen atom of the acetyl group does not participate in coordination.     

The preparation and characterization of mono- and bis-chelated cadmium(II) complexes of the di-2-pyridylketone Schiff base of S-methyldithiocarbazate (Hdpksme) and the X-ray crystal structure of the [Cd(dpksme)2] · 0.5 MeOH complex

New cadmium(II) complexes of empirical formulae, [Cd(dpksme)X] (dpksme = anionic form of the Schiff base; X = NCS^–, Cl^–, I^–) and [Cd(dpksme)₂] · 0.5MeOH, respectively have been prepared and characterized. The mono-ligated cadmium(II) complexes, [Cd(dpksme)X] are four-coordinate and tetrahedral but the bis-ligand complex, [Cd(dpksme)₂] · 0.5MeOH is six-coordinate and octahedral. The crystal and molecular structure of [Cd(dpksme)₂] · 0.5MeOH has been determined by X-ray diffraction. The complex has a distorted mer-octahedral structure in which the ligands are coordinated as uninegatively charged tridentate chelating agents via the pyridine nitrogen atoms, the azomethine nitrogen atoms and the thiolate sulfur atoms. The distortion from regular octahedral geometry is ascribed to the restricted bite angles of the ligands. The Schiff base and its cadmium(II) complexes exhibit mild antibacterial activities against Shigella dysenteriae, Bacillus cereus, Staphylococcus aureus and Escherichia coli. They are also mildly fungitoxic against the phytopathogenic fungi, Alternaria alternata and Macrophomina phaseolina.     

Efficient eco-friendly syntheses of dithiocarbazates and thiosemicarbazones

ABSTRACT

Eight Schiff bases have been synthesized by conventional and three different eco-friendly methods, whereby two aromatic carbonyl compounds viz. 2-thiophenecarboxaldehyde and salicylaldehyde were reacted with S-methyl, S-benzyl, and S-n-octyl-dithiocarbazates and thiosemicarbazide. In order to evaluate the efficiency of the synthesis methods, the time to complete the reaction and the yield of the Schiff base synthezised by eco-friendly methods, such as solvent-free grinding, water as a solvent, and lemon juice as catalyst, were compared with those synthesized by the conventional method. The chemical structures of all the synthesized Schiff bases, where two of them are novel and reported for the first time, were fully characterized by a variety of physico-chemical, analytical, and spectroscopic techniques. The molecular and crystal structures of the Schiff bases especially those having 2-thiophene moiety were further elucidated by single crystal X-ray diffraction analyzes.     

Superparallel holographic correlator for ultrafast database searches

We describe a superparallel holographic optical correlator that performs two-dimensional spatial and angular multiplexing simultaneously. The key step in this architecture is the use of a holographic multiplexer to split a query image into many copies before it applies them to the holographic database. A holographic demultiplexer, in conjunction with an aperture, is used to identify the location and the angle of the brightest correlation peak. This architecture uses only O(square root of N) detector elements to search through N unsorted images in a single query. We demonstrate the basic features of this architecture, using three spatial locations with eight angle-multiplexed images in each location.     

Dissipation rate correction methods

Dissipation rates of the turbulent kinetic energy and of the scalar variance are underestimated when the measurement resolution of the small scales of a turbulent flow field are insufficient. Results are presented of experiments conducted in a salt-stratified water tunnel (Schmidt number ∼700). Dissipation rates are determined to be underestimated, and thus correction techniques based on velocity structure functions and mixed-moment functions are proposed. Dissipation rates in laboratory experiments of shear-free, grid-generated turbulence are determined from balance calculations of the kinetic energy and scalar variance evolution equations. Comparisons between the structure function and balance estimates of dissipation show that the corrections are O(1) for the kinetic energy dissipation rate, and are O(100) for the scalar variance dissipation rate. This difference is due to the lack of resolution down to the Batchelor scales that is required for a high Schmidt number flow. Simple correction functions based on microscale Reynolds numbers are developed for both turbulent kinetic energy and scalar variance dissipation rates. Application of the technique to the results of laboratory experiments of density stratified turbulence, sheared turbulence, and sheared density stratified turbulence yields successful corrections. It is also demonstrated that the Karman–Howarth equality (and the analogous Yaglom equation) that relates second and third-order structure functions to dissipation rates is valid for both unstrained (decaying grid-generated turbulence) and density stratified and sheared turbulence at least up to the magnitudes of strains of the current experiments Nt∼10, St∼10, respectively. This is helpful for it allows the use of these equations in the analysis of turbulence even when the large scale background profiles of velocity and scalar are unknown.     

Synthesis,spectroscopy, and X-ray crystal structures of copper(II) complexes of the tridentate ONS ligand formed by condensation of 4,4,4-trifluoro-1-(2-thienyl)-2,4-butanedione with S-benzyldithiocarbazate

A new tridentate ONS ligand, H₂L, has been synthesized by condensing thenoyltrifluoroacetone(4,4,4-trifluoro-1-(2-thienyl)-2,4butaneanedione) with S-benzyldithiocarbazate and its structure determined by X-ray diffraction. In the solid state, the Schiff base exists as the ketoamine-thioketo tautomer but in solution and in the presence of copper(II), it converts to the enol-thiol form and deprotonates to give copper(II) complexes of formula, [CuL] and [CuLL¹] (L = doubly deprotonated form of the ligand; L¹ = py, bipy or phen] which have been characterized by magnetic, spectroscopic, and X-ray diffraction studies. An X-ray crystallographic analysis shows that [CuL(py)] has a square-planar geometry with the ligand coordinated to the copper(II) center via the enolate oxygen, the azomethinic nitrogen and the thiolate sulfur, the fourth coordination position being occupied by pyridine. The [CuL(bipy)] complex is five-coordinate with a structure close to square-pyramidal in which the Schiff base acts as a doubly deprotonated tridentate ONS ligand and bipy is bidentate.