Effect of the chemical structure of a tetradentate equatorial ligand on the spin-crossover properties of the Fe (III) complexes chain structures: Electron paramagnetic resonance study.

The effect of the chemical structure of the equatorial ligand on the spin state of the Fe (III) ion in a series of 1-D chain complexes of the general formula [Fe(L)(tvp)]BPh4 ·nCH3 OH, where L = dianions of Schiff base containing a different number of aromatic groups: N,N'-ethylenebis (salicylaldimine) (salen) 1, N,N'-ethylenebis (acetylacetone)2,2'-imine (acen) 2, N,N'-ethylenebis (benzoylacetylacetone)2,2'-imine (bzacen) 3, and tvp = 1,2-di(4-pyridyl)ethylene, was studied by ultraviolet-visible (UV-vis) and electron paramagnetic resonance (EPR) methods. The values of exchange interactions, thermodynamic parameters of spin-crossover, and electronic structure features of the Fe (III) complexes were estimated from the EPR data. The substitution of a fragment of the equatorial ligand L in the series salen-acen-bzacen changes the local symmetry of the complex in the 1-D chain, thereby affecting the spin variable properties.

Photoisomerization of 1,2-Di(4-pyridyl)ethylene According to NMR and UV Spectroscopy Data and Density Functional Modeling.

Photoisomerization of 1,2-di(4-pyridyl)ethylene under UV irradiation was studied by NMR and UV spectroscopy in solutions of acetone, acetonitrile and chloroform. It has been established that in the studied solutions under irradiation, geometric photoisomerization occurs: the trans-isomer transforms into the cis-isomer and then cyclization occurs. DFT modeling of the listed processes, states and UV absorption spectra of the sample in an acetonitrile solution was performed.

Predicting the Potentiometric Sensitivity of Membrane Sensors Based on Modified Diphenylphosphoryl Acetamide Ionophores with QSPR Modeling.

While potentiometric, plasticized membrane sensors are known as convenient, portable and inexpensive analytical instruments, their development is time- and resource-consuming, with a poorly predictable outcome. In this study, we investigated the applicability of the QSPR (quantitative structure-property relationship) method for predicting the potentiometric sensitivity of plasticized polymeric membrane sensors, using the ionophore chemical structure as model input. The QSPR model was based on the literature data on sensitivity, from previously studied, structurally similar ionophores, and it has shown reasonably good metrics in relating ionophore structures to their sensitivities towards Cu2+, Cd2+ and Pb2+. The model predictions for four newly synthesized diphenylphosphoryl acetamide ionophores were compared with real potentiometric experimental data for these ionophores, and satisfactory agreement was observed, implying the validity of the proposed approach.

Synergistic Solvent Extraction of Lanthanides(III) with Mixtures of 4-Benzoyl-3-Methyl-1-Phenyl-5-Pyrazolone and Phosphoryl-Containing Podands.

The solvent extraction of La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu from weak acidic chloride solutions into an organic phase containing 4-benzoyl-3-methyl-1-phenyl-5-pyrazolone (HP) and phosphoryl-containing podands (L) has been studied. A considerable synergistic effect was observed in the presence of neutral ligands L in the organic phase containing HP. The stoichiometry of the Ln(III) extracted species was determined by slope analysis and the equilibrium constants were calculated. It was found that the lanthanide(III) ions are extracted with mixtures of HP and neutral ligands in toluene from weak acidic solutions as LnLP3 complexes.

Measurement of J-couplings between chemically equivalent nuclei using off-resonance decoupling.

The method of measuring J-couplings between chemically equivalent nuclei in isotopically/magnetically non-equivalent environment, based on off-resonance decoupling, is described. The approach uses intensities, rather than frequencies of the spectral peaks and, therefore, the accuracy of measurement is not limited by spectral resolution.

Measuring the deformation of a ferrogel sphere in a homogeneous magnetic field.

A sphere of a ferrogel is exposed to a homogeneous magnetic field. In accordance to theoretical predictions, it gets elongated along the field lines. The time dependence of the elastic shear modulus causes the elongation to increase with time, similar to mechanic creep experiments, and the rapid excitation causes the sphere to vibrate. Both phenomena can be well described by a damped harmonic oscillator model. By comparing the elongation along the field to the contraction perpendicular to it, we can calculate Poisson's ratio of the gel. The magnitude of the elongation is compared to the theoretical predictions for elastic spheres in homogeneous fields.