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A dichlorophenyl substituted nitronyl nitroxide radical 2-(2,6-dichlorophenyl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazole-3-oxide-1-oxyl (L) is prepared, its structure and magnetic properties are studied. It is shown that the interaction of bis(hexafluoroacetylacetonato)copper(II) [Cu(hfac)2] with L leads to the formation of the {[Cu(hfac)2][Cu(hfac)2L2]} heterospin complex whose crystal structure consists of pseudo-polymer chains formed by alternating single-spin [Cu(hfac)2] and three-spin [Cu(hfac)2L2] fragments. It is established that the temperature dependence of magnetic susceptibility of {[Cu(hfac)2][Cu(hfac)2L2]} is determined by ferromagnetic exchange interactions between unpaired electrons of Cu(II) ions and the axially coordinated L in three-spin fragments. [ABSTRACT FROM AUTHOR]

The ternary TaIr2B2 boride was prepared by the reaction between iridium and TaB2 powders. It was shown that a choice in favor of any crystal structure of TaIr2B2 boride using only X-ray powder diffraction analysis and single-crystal XRD is rather difficult to make. The DFT calculations were carried out to predict the energetically preferred crystal structure of TaIr2B2. The 11B solid-state NMR spectrum of TaIr2B2 was recorded for the first time. A combination of diffraction and spectroscopic methods, as well as theoretical calculations, allowed us to make clear choice in favor of the triclinic space group for the crystal structure of TaIr2B2. The Vickers microhardness value for TaIr2B2 was found to be 17.9 ± 2.3 GPa, and the ternary TaIr2B2 boride can be considered a hard material. Therefore, the family of hard ternary boride phases got a new member. The coefficients of thermal expansion of TaIr2B2 measured by in situ high-temperature XRD analysis are independent of temperature along the a and b axes, but the CTE along the c axis deviates noticeably at elevated temperatures. The findings for the new ternary TaIr2B2 boride are of interest for the rational design of complex structural materials containing Ta–Ir–B-based components and prediction of their high-temperature behavior. Further research into this ternary boride as well as other iridium-containing ternary borides will provide a tool to solve the problems faced by high-temperature materials science. [ABSTRACT FROM AUTHOR]

A method for the synthesis of solvates of dinuclear heterospin complexes of bis(hexafluoroacetylacetonato)copper(ii) with 2-(4-methylpyridin-3-yl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazole-3-oxide-1-oxyl (LMe) and 2-(4-ethylpyridin-3-yl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazole-3-oxide-1-oxyl (LEt) of the composition [Cu(hfac)2LR]2 · Solv (Solv = benzene, bromobenzene, toluene, o-xylene, p-xylene) was developed. It was found that a decrease in temperature induces structural transformations of the solid phases of the complexes followed by significant changes in the distances between the paramagnetic centers in the intramolecular exchange clusters {Cu2+-O·-} from 2.321 to 1.974 Å. As a result, the temperature dependences of the effective magnetic moment μeff(T) exhibit magnetic features similar to spin transitions. An analysis of the shape of the μeff(T) curves suggested that the magnetic properties of the compounds under study depend primarily on the molecular packing. A comparison of the magneto-structural correlations typical of the [Cu(hfac)2LR]2 · Solv complexes studied in this work with the data obtained earlier for analogous solvates of heterospin polymer chain complexes showed that the spin transition characteristics of the [Cu(hfac)2LR]2 · Solv systems are much less sensitive to the change of the solvent than the corresponding characteristics of the heterospin polymers containing solvate molecules in the interchain space. The magnetic characteristics of the heterospin dimer molecules depend primarily on which cavity between the dimers is filled with solvate molecules. For solvates with monoclinic symmetry, changes in the solvent molecules occupying same-type cavities have almost no effect on the spin transition characteristics in the heterospin exchange cluster. [ABSTRACT FROM AUTHOR]

Hydrolysis of [M4(hfac)4(MeO)4(MeOH)4] (М = Сo, Ni and hfac is hexafluoroacetylaceton ate) is a convenient way of obtaining polynuclear complexes [Ni7(hfac)6(OH)8(H2O)6]•2H2O, [Co12(hfac)10(OH)14(H2O)8]•2H2O•2MePh, [Co12(hfac)10(OH)14(H2O)4(Me2CO)4]•3PhMe, and [Co12(hfac)10(OH)14(H2O)6(Me2CO)2]•2H2O•2Me2CO, whose structures were confirmed by X-ray analysis. [ABSTRACT FROM AUTHOR]

Alkali metals form mutinuclear compounds with redox-active singly and doubly reduced derivatives of sterically of hindered о-benzoquinones. Complexes [Na6(Cat)3(THF)7]•4THF, [Na5(Cat)2(SQ)(THF)5], [Na4(SQ)4(THF)4]•THF•C6H14, [Na4(3,5-SQ)4(THF)4], [K4(SQ)4(THF)4]•4THF and [Li3(SQ)3(THF)3]•THF (Cat is catecholate, SQ is semiquinonate) possessing high sensitivity to atmospheric oxygen were synthesized and their structures were determined. Magnetochemical measurements and quantum chemical calculations revealed that variation of the alkali metal and/or change in the structure of the polymetallic core significantly affect the energy of exchange interaction between the unpaired electrons of the paramagnetic ligands framing the polynuclear metal core formed by s-elements. [ABSTRACT FROM AUTHOR]