Hydrogen bonding-based 3D supramolecular architecture of [Cu(CHA)2][TCM]·11H2O

Reaction of Na₄TCM (1) (H₄TCM = tetra[4-(carboxyphenyl)oxamethyl]methane) with [Cu(CHA)](ClO₄)₂ (2)(CHA = 1,3,6,8,11,14-hexaaz atricyclo[12.2.1.1.^8,11] octadecane) in a DMF-water mixture yields [Cu(CHA)]₂[TCM] (3). Structural analysis of [Cu(CHA)]₂[TCM]·11H₂O (3·11H₂O) by single crystal X-ray diffraction reveals strong copper-oxygen bonds between two complex cations and the tetraanion leading to a 3D coordination network (zwitterionic structure), consolidated through additional NH...O=C hydrogen bonding within the cation/anion association. The resulting coordination geometry around a copper atom is a distorted square pyramidal with an oxygen atom of the anionic ligand in the apical position. A 3D supramolecular network is developed in the crystal based only on NH...OC hydrogen bonds between the macrocyclic metallic tecton and the carboxylate groups of neighboring 3D coordinated (zwitterionic) moieties. The pseudotetrahedral TCM^4? tetraanionic ligand induces a diamondoid architecture formed of large distorted adamantanoid cages.      

The synthesis, structure and physical properties of lanthanide(III) complexes with nicotinic acid

This article reports the synthesis of novel, rare-earth coordination complexes with nicotinic acid. Three compounds with the general formula Ln₂[(C₅H₄NCOO)₆(H₂O)₄] (Ln = Yb, 1; Ln = Gd, 2; Ln = Nd, 3) were prepared from relatively cheap and readily available reactants. Their compositions and structure were characterized by IR spectroscopy and single-crystal X-ray diffraction. The magnetic and thermogravimetric properties were also studied. The complexes consist of centrosymetric, dimeric molecules having all six nicotinato ligands coordinated with the central atom in the bidentate mode. The coordination environment of the Ln³⁺ for all three compounds is 8. Here we describe the crystal structure of Yb and Gd complexes with nicotinic acid.      

Crystallographic and structural characterization of heterometallic platinum compounds part IV: heterotetranuclear clusters

This review includes over two hundred heterotetranuclear platinum clusters. The clusters are of the compositions Pt₃M, Pt₃M₂, PtM₃, Pt′₂MM′, PtM₂M′ and PtMM′M”. There are twenty five different M atoms (transition and non-transition) as a partner(s) of platinum. The four metal atoms are found in a tetrahedral, planar-rhombohedral, butterfly, spited-triangular, cubane, eight — and oligo-membered rings and a unique structures. There is wide variety of the ligands from uni to- undecadentate, with the most common P and C donor sites. The shortest Pt-M (transition) versus Pt-M (non-transition) bond distances are 2.4833(8)Å (M=Pd) vs. 2.4365(5)Å (Ge). Several relationships between the various structural parameters were found and are discussed.      

Crystallographic and structural characterization of heterometallic platinum complexes Part V. Heteropentanuclear complexes

This review classifies and analyzes over eighty heteropentanuclear Pt complexes. There are eight types of metal combinations: Pt₄M, Pt₃M₂, Pt₂M₃, PtM₄, Pt₃MM′, Pt₂M₂M′, PtM₂M′₂ and PtM₃M′. The five metal atoms are in a wide variety of arrangements: trigonal-bipyramidal (most common), square-pyramidal, spike-triangular, butterfly, cubane, linear and one unique. Platinum bonds to a variety of triad partner metal atoms, soft, through borderline to hard. The shortest Pt-M bond distances for non-transition and transition M are 2.406(4) Å (M = Ge) and 2.30(1) Å (M = Co). The shortest Pt-Pt bond distance is 2.580(1) Å. Several relationships between the structural parameters were found and are discussed. Several complexes exist in two isomeric forms and others contain two crystallographically independent molecules. Both the isomers as well as independent molecules are examples of distortion isomerism.      

Characterization of the citrate precursor, used for synthesis of nanosized Mg-Zn ferrites

The citrate precursor has been used to synthesize nanocrystalline Mg-Zn-ferrites. The nature of the prepared precursor is characterized and compared with those of the precursors studied earlier, prepared by the same process. The study has been performed by inorganic and organic elemental analyses, Fourier Transformed Infrared Spectroscopy (FTIR), Mössbauer spectroscopy, X-ray Photoelectron Spectroscopy (XPS), Electron Paramagnetic Resonance (EPR), Electronic absorption spectrometry in the UV-VIS region, Differential Thermal analysis/ Thermogravimetry (DTA-TG) analyses, and X-ray diffraction (XRD) analysis. The collected results determined the precursor as a coordination polymer with monomer unit (NH₄)₄{M [Fe(C₆H₅O₇)₂]₂}, where M=Zn or Mg.      

Stereoselective preparation of mono- and bis-derivatives of pentacyclo[6.3.0.02,6.03,10.05,9] undecane (D 3-trishomocubane)

The rearrangement of easily accessible Cookson’s diketone with chlorosulfonic acid in chloroform followed by the acidic hydrolysis gave 6-chloro-7-hydroxy-dichloropentacyclo[6.3.0.0^2,6.0^3,10.0^5,9]undecane-4-one, whose syn-stereochemistry was assigned through the X-ray crystal structure analysis. This key structure was used for the stereoselective synthesis of the D ₃-trishomocubane derivatives as well as for the preparation of potential drugs bearing hydroxy- and amino-functional groups. A new multigram preparative synthesis of D ₃-trishomocubane was developed.      

Copper-cobalt ferrites as catalysts for methanol decomposition

Copper-cobalt ferrites with composition Cu_1?xCo_xFe₂O₄, where x= 0.2 and 0.8 were prepared by thermal treatment of co-precipitated precursor. The obtained materials were characterized by TG-DSC, XRD, Transmission and Conversion Electron Mössbauer spectroscopy and temperature programmed reduction with hydrogen. The catalytic properties of ferrites were tested in methanol decomposition to CO and hydrogen.      

Investigation of electrical properties of PANI/chalcogenide junctions

Pure Polyaniline (EB) and Polyaniline doped with different protonic acids (ESs) were chemically synthesized using ammonium peroxydisulphate (APS) as an oxidant. Junctions have been prepared by evaporating chalcogenide materials (ZnSe, CdSe) on conducting polyaniline (EB & ESs) pellets using a vacuum evaporation technique. I–V characteristics of junctions have been studied at room temperature using the Keithley electrometer 6517A. I–V measurements show the rectification effect. A junction of ES[PO₄ ^3?] may be preferred over the other junctions due to its low ideality factor and maximum rectification ratio.      

Regio- and stereoselectivity of polar [2+3] cycloaddition reactions between (Z)-C-(3,4,5-trimethoxyphenyl)-N-methylnitrone and selected (E)-2-substituted nitroethenes

[2+3] Cycloaddition reactions of the highly reactive (Z)-C-(3,4,5-trimethoxyphenyl)-N-methylnitrone with (E)-2-R-nitroethenes proceed under mild conditions and yield mixtures of stereoisomeric 2-methyl-3-(3,4,5-trimethoxyphenyl)-4-nitro-5-R-isoxazolidines. The effect of regiospecificity of the cycloadditions may be accounted for by the theory of electrophilicity indexes. Stereoselectivity, however, is determined by a compilation of steric and secondary orbital effects.      

Decomposition of oxalate by hydrogen peroxide in aqueous solution

The decomposition rate of oxalate by hydrogen peroxide has been investigated by a KMnO₄ titration method. The rate equation for decomposition of hydrogen peroxide in the aqueous phase is 1n([H₂O₂]/[H₂O₂]₀)=?k₁·t, where k₁=0.2, for [H⁺]<2M, k₁=0.2+0.34([H⁺]?2), for [H⁺]>2M. As the acidity increases over 2M, an acid catalysis effect appeard. The new rate equation proposed for the decomposition of oxalate by hydrogen peroxide is $$ - \frac{d}{{dt}}X_{[OX]} = k_2 [H_2 O_2 ]_0 (1 - X_{[OX]} )(e^{ - k_1 t} - \frac{{[OX]_0 }}{{[H_2 O_2 ]_0 }}X_{[OX]} )$$ The rate constant for decomposition of oxalate, k₂, increased with nitric acid concentration and the effect of hydrogen ion concentration was expressed as k₂=a[H⁺]ⁿ, where the values fora andn were a=1.54, n=0.3 at [H⁺]<2M, a=0.31, n=2.5 at [H⁺]>2M, respectively.     

Cobalt electrodeposition onto polycrystalline gold from ammoniacal solutions

In the present work, the cobalt electrodeposition onto polycrystalline gold electrodes from aqueous solutions containing 0.01M CoSO₄ + 1 M (NH₄)₂SO₄ at pH=7 was analyzed. Linear voltammetry results suggested a change in the kinetic of the cobalt electrodeposition. In all cases, the nucleation rate (A), the number of active nucleation sites (N ₀) and the saturation number of nuclei (N _s ) values were potential dependent. The calculated Gibbs free energy (ΔG) for this system was 1.88×10^?20 J nuclei^?1 and the transfer coefficient for the Hydrogen Electroreduction Reaction (HER) was 0.47.      

Extraction properties of β-aminophosphine oxides towards lanthanides and alkaline earth metals

The investigation of the extraction properties of a series of polyoligodentate β-aminophosphine oxides 1–8 bearing from one to six phosphine oxide groups in a molecule towards Ln(III) and alkaline earth metals ions from neutral media has revealed that, using common diluents, the extraction efficiency increases with an increase of a number of P=O functions in a ligand. The addition of ionic liquid, namely 1-butyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide ([bmim][NTf₂]), significantly increasing the extraction efficiency and application of IL concentration of 0.05 M (in 1,2-dichloroethane) providing the maximum recovery of metal ions with Lu/La separation factor reaching up to 91. Hexapodal tris[bis(2-diphenylphosphorylethyl)aminoethyl]amine 8 demonstrates the highest extraction under all conditions applied and the separation factor for U and Eu of this compound exceeded 10³.      

The use of ultrasonic treatment for improvement of metrological performance of sorption atomic absorption determination of lead(II) and cadmium(II) traces

The optimal parameters for ultrasonic treatment (frequency 200–300 kHz, intensity 2–4 W cm^?2) were obtained to intensify Pb(II) and Cd(II) sorption concentration by carbon sorbent from apricot pit. The combined action of ultrasonic frequency of 18 kHz and 1 MHz on concentrate slurry increases its sedimentation stability from 3 to 180 minutes and decreases S_r value up to 7% at Pb(II), Cd(II) hybrid sorption atomic absorption determination in natural waters, brines, common salt.      

Synthesis of new (arylcarbonyloxy)aminopropanol derivatives and the determination of their physico-chemical properties

Eight hydrochlorides of 3-{2-[(2/4-fluorophenoxy)-ethylamino]}-2-hydroxypropyl-4-alkoxybenzoates and four hydrochlorides of 3-tert-butylamino-2-hydroxypropyl-4-butoxybenzoates were prepared as potential antagonists of the β₁-adrenergic receptor (beta-blockers). A multistep synthesis of these compounds is described as well as their detailed analytical characterization. The pharmacokinetic properties of these weak base compounds are significantly influenced by their acid-base dissociation constant, pK _a. The knowledge of this value is crucial for new drug development. This paper is aimed at developing a methodology that utilizes pH-dependent ¹H NMR spectroscopy for its routine analysis. The selected predicted physico-chemical parameters of the new (arylcarbonyloxy)aminopropanols (i.e., aryloxyaminopropanol derivatives) were compared with the model drugs esmolol and flestolol.      

Spectrophotometric study of competitive complexation equilibria involving overlapped spectral responding species: Determination of the stability constant of bismuth-pyrophosphate complex

Spectrophotometric study of competitive complex formation equilibria involving overlapped spectral responding species applying a simple and versatile algorithm was carried out. The algorithm involves multivariable regression for calculation of equilibrium concentrations from multiwavelength data and mass action law for the stability constant calculation. The used regression functions are part of common statistical software. Stability constants and complex stoichiometry of competing equilibria were simultaneously determined. The species concentration profiles at several spectral overlapping and ??-coefficient of competing reaction were obtained. Non-absorbing bismuth ?? pyrophosphate (PPh) system was studied as a competitive reaction of bismuth ?? 4-(2-Pyridylazo) resorcinol (PAR) complex. The formation of Bi-PPh complex with 1:1 stoichiometry was proved in the studied concentration region (C_Bi = 1×10^?5 mol L^?1; C_PPh = 5×10^?6 ? 1×10^?4 mol L^?1). The stability constant of the complex at pH 1 and ?? = 1.0 have been determined: log?? = 4.2±0.2.      

Lumineszenzspektren von ein- und zweikernigen Chrom(III)-Glycin-Komplexverbindungen

The luminescence spectra of the polycrystalline compounds [Cr(CH₂NH₂COO)₃ · H₂O] and [Cr₂(OH)₂(CH₂NH₂COO)₄] are investigated in the temperature range of 120K – 4.2K. From the known crystal structure (P2_1/c =D _2h ^/5 ) of the mononuclear compound assignment of the zero-phonon bands based on crystal field theory becomes possible. Both of the highly intense phosphorescence transitions are observed at \(P_1 = 14493 cm^{ - 1} ({}^2A'' \xrightarrow{{0.0}} {}^4A) and P_2 = 14428 cm^{ - 1} ({}^2A' \xrightarrow{{0.0}} {}^4A)\) . Assignment of the accompanying vibronic bands is made from the measured infrared data. Crystal field parameters Dq, B and C are determined from the luminescence and reflectance spectra. In the case of the binuclear compound the Cr³⁺-Cr³⁺ interaction via hydroxyl brides may be described by an axchange operator \(H_{ex} = - 2 \sum\limits_{ij} {J_{ij} S_i^a \cdot S_j^a } \) and from this the energy level diagram is calculated. Both observed strong phosphorescence bands at 14369 cm^?1 and 14184 cm^?1 are assigned to \(\left| {{}^2E \cdot {}^4A_2 \rangle _{s = 2} \xrightarrow{{0.0}}} \right| {}^4A_2 \cdot {}^4A_2 \rangle _{s = 2} and \left| {{}^2E \cdot {}^4A_2 \rangle _{s = 1} \xrightarrow{{0.0}}} \right| {}^4A_2 \cdot {}^4A_2 \rangle _{s = 1} \) transitions.     

Comparative studies of Pd, Ru, Ni, Cu/ZnAl2O4 catalysts for the water gas shift reaction

The activity of monometallic Pd, Ru, Ni and Cu catalysts supported on spinel ZnAl₂O₄ for water gas shift reaction (WGS) was investigated. The physicochemical properties of each catalyst was studied by XRD, TPR, BET and chemisorption methods. The highest activity was obtained for Cu/ZnAl₂O₄ among the catalysts tested. The activation process carried out in a reducing atmosphere 5%H₂-95%Ar in the case of Cu/ZnAl₂O₄ system lead to the catalytic activity improvement. In the case of copper catalysts, the water gas shift reaction proceeded by the redox surface mechanism between Cu⁰/Cu⁺. The PdZn alloy formation after reduction at 350°C was shown.      

Reaction of barbituric acid with organic azides and phosphonium ylides

Amination by organic azides has been carried out to provide aminobarbiturates by fusion of a triazole ring to the 5,6-positions of barbituric acid followed by cleavage and thermal elimination of nitrogen, whereas aza-Wittig reaction gave phosphoranylidene barbituric acid salts.