Effect of gas-chromatography column regeneration during the CHN/S analysis of copper-chromium disulfide

The effect of gas-chromatography column (GCC) regeneration during the CHN/S analysis of copper-chromium disulfide CuCrS2 (CCDS) samples on the Euro EA 3000 analyzer was identified. The effect results in a perfect straight baseline on the chromatograms of both CuCrS2 and standard samples. The obtained straight baseline causes high-quality peaks separation. In addition, the reported regeneration procedure reduces significantly the GCC regeneration duration that usually takes up to several days

Fist oxidovanadium complexes containing chiral derivatives of dihydrophenanthroline and diazafluorene

© 2017 Elsevier Ltd Reactions of VCl 3 with chiral derivatives of dihydrophenanthroline (2R,4R,9R,11R)-3,3,10,10-tetramethyl-1,2,3,4,6,7,9,10,11,12-decahydro-2,4:9,11-dimethanodibenzo[b,j][1,10] phenanthroline (L1) and diazafluorene (1R,3R,8R,10R)-2,2,9,9-tetramethyl-2,3,4,7,8,9,10,12-octahydro-1H-1,3:8,10-dimethanocyclopenta[1,2-b:5,4-b′]diquinoline (L2) in acetonitrile in air yield mixtures of [V III (L1/L2)(CH 3 CN)Cl 3 ] and [V IV O(L1/L2)(CH 3 CN)Cl 2 ] (I, II) which were characterized by elemental analysis, IR spectroscopy and magnetic susceptibility data. The behavior of these mixtures in different solvents was investigated by 51 V NMR and EPR spectroscopies as well as optical rotation. Recrystallization of a [V III (L1)(CH 3 CN)Cl 3 ]/[V IV O(L1)(CH 3 CN)Cl 2 ] mixture from CH 2 Cl 2 /Et 2 O affords a V(IV) complex, [V IV O(L1)(H 2 O)Cl 2 ]·nCH 2 Cl 2 (III). Recrystallization from MeOH/Et 2 O leads to complete oxidation to V(V) complex [V V O(L1)(OMe)Cl 2 ] (IV), which was characterized by X-ray crystallography, IR, 51 V and 1 H NMR spectroscopies

23-electron octahedral molybdenum cluster complex [{Mo 6 I 8 }Cl 6 ] –

Photoactive transition metal compounds that are prone to reversible redox reactions are important for myriad applications, including catalysis, optoelectronics and sensing. This article describes chemical and electro-chemical methods to prepare cluster complex (Bu4N)[{Mo6I8}Cl6], a rear example of 23ē cluster complex within the family of octahedral clusters of Mo, W, and Re. The low temperature and room temperature crystal structures, electronic structure and the magnetic, optical and electrochemical properties of this complex are described

Effect of the Order-Disorder Transition on the Electronic Structure and Physical Properties of Layered CuCrS2

The work reports a comprehensive study of the Seebeck coefficient, electrical resistivity and heat capacity of CuCrS2 in a wide temperature range of 100–740 K. It was shown that the value of the Seebeck coefficient is significantly affected by the sample treatment procedure. The order-to-disorder (ODT) phase transition was found to cause a metal-insulator transition (MIT). It was established that the ODT diminishes the Seebeck coefficient at high temperatures (T > 700 K). The DFT calculations of the CuCrS2 electronic structure showed that the localization of copper atoms in octahedral sites makes the band gap vanish due to the MIT. The decrease of CuCrS2 electrical resistivity in the ODT temperature region corresponds to the MIT

Magnetic Properties of Novel Layered Disulfides CuCr0.99Ln0.01S2 (Ln = La…Lu)

The comprehensive study of the lanthanide-doped solid solutions CuCr0.99Ln0.01S2 (Ln = La…Lu) magnetic properties was carried out using static magnetochemistry and differential scanning calorimetry techniques. It was shown that magnetic properties of CuCr0.99Ln0.01S2 are significantly affected by the magnetic properties of the lanthanide ion. The magnetic susceptibility and the effective magnetic moment were found to deviate from the Curie-Weiss law in the temperature 90 K below and 50 K above the order-disorder transition at 695 K. The observed behavior of the temperature dependence of the effective magnetic moment in the order-disorder transition temperature region was described as a result of copper atoms redistribution over different types of the crystallographic sites

Fist oxidovanadium complexes containing chiral derivatives of dihydrophenanthroline and diazafluorene

© 2017 Elsevier Ltd Reactions of VCl 3 with chiral derivatives of dihydrophenanthroline (2R,4R,9R,11R)-3,3,10,10-tetramethyl-1,2,3,4,6,7,9,10,11,12-decahydro-2,4:9,11-dimethanodibenzo[b,j][1,10] phenanthroline (L1) and diazafluorene (1R,3R,8R,10R)-2,2,9,9-tetramethyl-2,3,4,7,8,9,10,12-octahydro-1H-1,3:8,10-dimethanocyclopenta[1,2-b:5,4-b′]diquinoline (L2) in acetonitrile in air yield mixtures of [V III (L1/L2)(CH 3 CN)Cl 3 ] and [V IV O(L1/L2)(CH 3 CN)Cl 2 ] (I, II) which were characterized by elemental analysis, IR spectroscopy and magnetic susceptibility data. The behavior of these mixtures in different solvents was investigated by 51 V NMR and EPR spectroscopies as well as optical rotation. Recrystallization of a [V III (L1)(CH 3 CN)Cl 3 ]/[V IV O(L1)(CH 3 CN)Cl 2 ] mixture from CH 2 Cl 2 /Et 2 O affords a V(IV) complex, [V IV O(L1)(H 2 O)Cl 2 ]·nCH 2 Cl 2 (III). Recrystallization from MeOH/Et 2 O leads to complete oxidation to V(V) complex [V V O(L1)(OMe)Cl 2 ] (IV), which was characterized by X-ray crystallography, IR, 51 V and 1 H NMR spectroscopies

Fist oxidovanadium complexes containing chiral derivatives of dihydrophenanthroline and diazafluorene

© 2017 Elsevier Ltd Reactions of VCl 3 with chiral derivatives of dihydrophenanthroline (2R,4R,9R,11R)-3,3,10,10-tetramethyl-1,2,3,4,6,7,9,10,11,12-decahydro-2,4:9,11-dimethanodibenzo[b,j][1,10] phenanthroline (L1) and diazafluorene (1R,3R,8R,10R)-2,2,9,9-tetramethyl-2,3,4,7,8,9,10,12-octahydro-1H-1,3:8,10-dimethanocyclopenta[1,2-b:5,4-b′]diquinoline (L2) in acetonitrile in air yield mixtures of [V III (L1/L2)(CH 3 CN)Cl 3 ] and [V IV O(L1/L2)(CH 3 CN)Cl 2 ] (I, II) which were characterized by elemental analysis, IR spectroscopy and magnetic susceptibility data. The behavior of these mixtures in different solvents was investigated by 51 V NMR and EPR spectroscopies as well as optical rotation. Recrystallization of a [V III (L1)(CH 3 CN)Cl 3 ]/[V IV O(L1)(CH 3 CN)Cl 2 ] mixture from CH 2 Cl 2 /Et 2 O affords a V(IV) complex, [V IV O(L1)(H 2 O)Cl 2 ]·nCH 2 Cl 2 (III). Recrystallization from MeOH/Et 2 O leads to complete oxidation to V(V) complex [V V O(L1)(OMe)Cl 2 ] (IV), which was characterized by X-ray crystallography, IR, 51 V and 1 H NMR spectroscopies

Fist oxidovanadium complexes containing chiral derivatives of dihydrophenanthroline and diazafluorene

© 2017 Elsevier Ltd Reactions of VCl 3 with chiral derivatives of dihydrophenanthroline (2R,4R,9R,11R)-3,3,10,10-tetramethyl-1,2,3,4,6,7,9,10,11,12-decahydro-2,4:9,11-dimethanodibenzo[b,j][1,10] phenanthroline (L1) and diazafluorene (1R,3R,8R,10R)-2,2,9,9-tetramethyl-2,3,4,7,8,9,10,12-octahydro-1H-1,3:8,10-dimethanocyclopenta[1,2-b:5,4-b′]diquinoline (L2) in acetonitrile in air yield mixtures of [V III (L1/L2)(CH 3 CN)Cl 3 ] and [V IV O(L1/L2)(CH 3 CN)Cl 2 ] (I, II) which were characterized by elemental analysis, IR spectroscopy and magnetic susceptibility data. The behavior of these mixtures in different solvents was investigated by 51 V NMR and EPR spectroscopies as well as optical rotation. Recrystallization of a [V III (L1)(CH 3 CN)Cl 3 ]/[V IV O(L1)(CH 3 CN)Cl 2 ] mixture from CH 2 Cl 2 /Et 2 O affords a V(IV) complex, [V IV O(L1)(H 2 O)Cl 2 ]·nCH 2 Cl 2 (III). Recrystallization from MeOH/Et 2 O leads to complete oxidation to V(V) complex [V V O(L1)(OMe)Cl 2 ] (IV), which was characterized by X-ray crystallography, IR, 51 V and 1 H NMR spectroscopies

Charge Distribution in Layered Lanthanide-Doped CuCr_0.99Ln_0.01S₂ (Ln = Pr–Tb) Thermoelectric Materials

The charge distribution study of metal atoms in CuCr0.99Ln0.01S2 (Ln = Pr–Tb) solid solutions was carried out using X-ray photoelectron spectroscopy (XPS). The analysis of the binding energy of S2p, Cu2p, Cr2p, Ln3d and Ln4d levels allows one to determine the oxidation state of atoms. Copper atoms were found to be monovalent. Chromium and lanthanide atoms were found to be in the trivalent state. Sulfur atoms were found to be in the divalent state. Cationic substitution was found to occur via an isovalent mechanism of Cr3+ to Ln3+. The obtained results were used for the interpretation of the Seebeck coefficient increase for CuCr0.99Ln0.01S2 solid solutions in contrast to the initial CuCrS2 matrix. The largest Seebeck coefficient values of 142 and 148 µV/K were observed at 500 K for CuCr0.99Sm0.01S2 and CuCr0.99Pr0.01S2, respectively. The obtained values are 1.4 times greater in comparison with those for the initial matrix (105 µV/K)

Chemical Diversity of Mo₅S₅ Clusters with Pyrazole: Synthesis, Redox and UV-vis-NIR Absorption Properties

The chemistry of transition metal clusters has been intensively developed in the last decades, leading to the preparation of a number of compounds with promising and practically useful properties. In this context, the present work demonstrates the preparation and study of the reactivity, i.e., the possibility of varying the ligand environment, of new square pyramidal molybdenum chalcogenide clusters [{Mo5(μ3-S)i4(μ4-S)i(μ-pz)i4}(pzH)t5]1+/2+ (pzH = pyrazole, i = inner, t = terminal). The one-step synthesis starting from the octahedral Mo6Br12 cluster as well as the substitution of the apical pyrazole ligand or the selective bromination of the inner pyrazolate ligands were demonstrated. All the obtained compounds were characterized in detail using a series of physicochemical methods both in solid state (X-ray diffraction analysis, etc.) and in solution (nuclear magnetic resonance spectroscopy, mass spectrometry, etc.). In this work, redox properties and absorption in the ultraviolet-visible and near-infrared region of the obtained compounds were studied