Pseudotetrahedral cobaltate(II) anions with two and three different kinds of ligands

New complexes of the general types HCo(NCS)₃ ·nL, HCoX ₂(NCS) ·nL and HCo(NCS)₂I ·nL (whereX=Cl, Br, I;L=diethyl ether, pyridine, aniline;n=1.5, 2, 3, 3.5) have been prepared and characterized. The magnetic and spectroscopic data indicate that pseudotetrahedral [Co(NCS)₃ L]^?, [CoX ₂(NCS)L]^? and [Co(NCS)₂IL]^? anions are present in the solid pyridine and aniline compounds.     

The first cobalt metallacrowns: preparation and characterization of mixed-valence cobalt(II/III), inverse 12-metallacrown-4 complexes

Aerobic reactions of Co(O(2)CMe)(2).4H(2)O with di-2-pyridyl ketone oxime (Hpko) in the presence of counterions (ClO(4)(-), PF(6-)) give the tetranuclear, mixed-valence cobalt(II/III) clusters [Co(II)(2)Co(III)(2)(OR)(2)(O(2)CMe)(2)(pko)(4)S(2)]X(2) [R = H, S = MeOH, X = ClO(4) (1); R = Me, S = EtOH, X = PF(6) (2)] depending on the solvent mixture. Complexes 1 and 2 are the first Co members in the family of metallacrowns adopting the extremely rare inverse 12-metallacrown-4 motif.     

Reductive decolorization of a textile reactive dyebath under methanogenic conditions

The objective of the present study was to assess the biological decolorization of an industrial, spent reactive dyebath and its three dye components (Reactive Blue 19 [RB 19], Reactive Blue 21 [RB 21], and Reactive Red 198 [RR 198]) under methanogenic conditions. Using a mixed, methanogenic culture, batch assays were performed to evaluate the rate and exten of color removal as well as any potential toxic effects. Overall, a high rate and extent of color removal (>10 mg/[L·h] and 88%, respectively) were observed in cultures amended with either RB19 (an anthraquinone dye) or spent dyebath at an initial dye concentration of 300 mg/L (expressed as RB 19 equivalent) and 30 g/L of NaCl. Inhibition of acidogenesis and, to a larger degree, of methanogenesis resulting in accumulation of volatile fatty acids was observed in both RB 19- and spent dyebath-amended cultures. RB 21 (a phthalocyanine dye) and RR 198 (an azo dye) tested at an initial concentration of 300 mg/L did not result in any significant inhibition of the mixed methanogenic culture. Based on results obtained with cultures amended with RB 19 with and without NaCl, as well as a control culture amended with 30 g/L of NaCl, salt was less inhibitory than either RB 19 or the dyebath. Therefore, the toxic effect of the spent dyebath is at least partially attributed to its major dye component RB 19 and NaCl. Further testing of the effect of RB 19 decolorization products on the methanogenic activity in the absence of NaCl demonstrated that these products are much less inhibitory than the parent dye. Although color removal occurred despite the severe culture inhibition, biological decolorization of full-strength reactive spent dyebaths using methanogenic cultures in a repetitive, closed-loop system is not deemed feasible. For this reason, a fermentative and halotolerant culture was developed and successfully used in our laboratory for the decolorization of industrial reactive dyebaths with 100 g/L of NaCl.     

Etherate,pyridine, and aniline compounds of the complex tri- and tetra-iodoacids of Zn(II) and Cd(II)

The preparation, for the first time, and the properties of the title compounds are described. Analytical conductometric, spectral (infrared and ultraviolet) and data from X-ray powder spectra yield information about the probable structure of the complexes in the solid state. The existence of metal-nitrogen bond for all pyridine and aniline complexes, except H₂CdI₄·4An (An=aniline), is adduced from infrared and far infrared spectral studies.

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Etherate, Pyridin- und Anilin-Verbindungen der komplexen Tri- und Tetra-Jodsäuren vonZn(II) undCd(II)

Zusammenfassung Die Darstellung und die Eigenschaften der Titelverbindungen werden erstmalig beschrieben. Analytische und konduktometrische Daten, sowie IR, UV und Röntgenpulveraufnahmen ergaben Informationen, aus denen die wahrscheinliche Struktur der Komplexe im festen Zustand abgeleitet wurde. Die Existenz von Metall—Stickstoff-Bindungen für alle Pyridin- und Anilin-Komplexe, mit Ausnahme von H₂CdI₄·4An (An=Anilin), ergibt sich aus den Daten von IR und fernem IR.

     

Using pyridine amidoximes in 3d-metal cluster chemistry: a novel ferromagnetic Ni12 complex from the use of pyridine-2-amidoxime

The use of pyridine-2-amidoxime in reaction with NiCl2.6H2O in the presence of NaOMe has led to a cationic NiII 12 cluster with novel structural features; each cluster molecule is a ferromagnet with a spin ground state of S = 6 arising from ferromagnetic exchange between the six octahedral NiII ions, but with intercationic interactions also affecting the magnetic properties.     

A family of enneanuclear iron(II) single-molecule magnets

Complexes [Fe₉(X)₂(O₂CMe)₈{(2‐py)₂CO₂}₄] (X^?=OH^? ( 1 ), N₃^? ( 2 ), and NCO^? ( 3 )) have been prepared by a route previously employed for the synthesis of analogous Co₉ and Ni₉ complexes, involving hydroxide substitution by pseudohalides (N₃^?, NCO^?). As indicated by DC magnetic susceptibility measurements, this substitution induced higher ferromagnetic couplings in complexes 2 and 3 , leading to higher ground spin states compared to that of 1 . Variable‐field experiments have shown that the ground state is not well isolated from excited states, as a result of which it cannot be unambiguously determined. AC susceptometry has revealed out‐of‐phase signals, which suggests that these complexes exhibit a slow relaxation of magnetization that follows Arrhenius behavior, as observed in single‐molecule magnets, with energy barriers of 41 K for 2 (τ₀=3.4×10^?12 s) and 44 K for 3 (τ₀=2.0×10^?11 s). Slow magnetic relaxation has also been observed by zero‐field ⁵⁷Fe Mössbauer spectroscopy. Characteristic integer‐spin electron paramagnetic resonance (EPR) signals have been observed at X‐band for 1 , whereas 2 and 3 were found to be EPR‐silent at this frequency. ¹H NMR spectrometry in CD₃CN has shown that complexes 1 – 3 are stable in solution.     

The interfacial properties of MgCl(2) thin films grown on Si(111)7 x 7

Photoelectron spectroscopy with synchrotron radiation and low energy electron diffraction (LEED) were used in order to study the MgCl(2)Si(111) system. At submonolayer coverage of MgCl(2), a new LEED pattern was observed corresponding to a (sqr rt 3 x sqr rt 3)R30 degrees overlayer superimposed on the underlying reconstructed Si(111)7 x 7. The surface species at this stage are mainly molecular MgCl(2) and MgCl(x) (x<2) or MgO(x)Cl(y) attached to the Si substrate through Cl bridges coexisting with monodentate SiCl. The interfacial interaction becomes more pronounced when the submonolayer coverage is obtained by annealing thicker MgCl(2) layers, whereby desorption of molecular MgCl(2) is observed leaving on the nonreconstructed silicon surface an approximately 0.2 ML thick MgCl(x) layer which again forms the (sqr rt 3 x sqr rt 3 )R30 degrees superstructure.     

Dynamic stall modelling on airfoils based on strong viscous–inviscid interaction coupling

The prediction of the aerodynamic performance of pitching airfoils in stall conditions is considered in the context of strong viscous–inviscid interaction modelling. The aim of the work is to demonstrate the capabilities of a low‐cost dynamic stall model well suited for engineering applications. The model is formulated on the basis of a standard panel method combined with a vortex blob approximation of the wake. The development of the boundary layer over the airfoil and the evolution of the shear layer in the wake are taken into account by means of strong viscous–inviscid interaction coupling. To this end a transpiration layer is added to the inviscid formulation which represents the displacement effect viscosity results in the flow while the non‐linear coupled equations are solved simultaneously. Separation is modelled by introducing a second wake originating from the separation point (‘double‐wake’ concept) which is provided as part of the boundary layer solution. The theoretical presentation of the model is supported with favourable comparisons to four sets of wind tunnel measurements. Copyright © 2007 John Wiley & Sons, Ltd.     

Synthesis,crystal structures and spectroscopic studies of calcium(II) succinamate(-1) complexes

The reaction of succinamic acid (H₂sucm) with Ca(NO₃)₂·4H₂O yielded compounds [Ca(Hsucm)(NO₃)(H₂O)]_n (1) and [Ca(Hsucm)₂]_n (2). The succinamate(-1) ligand presents two new ligation modes and coordinates through the two carboxylato and the amide O-atoms, thus bridging three Ca^II ions which assemble into zig-zag 1D chains in 1 and 2D networks in 2. Intermolecular hydrogen bonding interactions in the crystal structures of 1 and 2 result in overall 3D framework structures. Both compounds have been characterized by IR and ¹H NMR spectroscopy, and their thermal decomposition was monitored by TG/DTG and DSC measurements. The structural comparison of 1 and 2 with known lanthanide(III) succinamate(-1) complexes reveals differences in the coordination mode of the ligand and in the coordination number of the metal ions; the biological relevance of these differences is discussed.