A. L. Trigub

A Heterometallic (Fe6Na8) Cage-like Silsesquioxane: Synthesis, Structure, Spin Glass Behavior and High Catalytic Activity

The exotic “Asian Lantern” heterometallic cage silsesquioxane [(PhSiO1.5)20(FeO1.5)6(NaO0.5)8(n-BuOH)9.6(C7H8)] (I) was obtained and characterized by X-ray diffraction, EXAFS, topological analyses and DFT calculation. The magnetic property investigations revealed that it shows an unusual spin glass-like behavior induced by a particular triangular arrangement of Fe(III) ions. Cyclohexane and other alkanes as well as benzene can be oxidized to the corresponding alkyl hydroperoxides and phenol, respectively, by hydrogen peroxide in air in the presence of catalytic amounts of complex I and nitric acid. The I-catalyzed reaction of cyclohexane, c-C6H12, with H216O2 in an atmosphere of 18O2 gave a mixture of labeled and non-labeled cyclohexyl hydroperoxides, c-C6H11–16O–16OH and c-C6H11–18O–18OH, respectively, with an 18O incorporation level of ca. 12%. Compound I also revealed high efficiency in the oxidative amidation of alcohols into amides: in the presence of complex I, only 500 ppm of iron was allowed to reach TON and TOF values of 1660 and 92 h−1.

Heterometallic Na6Co3 Phenylsilsesquioxane Exhibiting Slow Dynamic Behavior in its Magnetization

A heterometallic phenylsilsesquioxane [(PhSiO1,5)22(CoO)3(NaO0.5)6]⋅(EtOH)6⋅(H2O) 1 cage architecture of Co(II) ions in a triangular topology exhibits a slow dynamic behavior in its magnetization, induced by the freezing of the spins of individual molecules.

Highly Luminescent, Water‐Soluble Lanthanide Fluorobenzoates: Syntheses, Structures and Photophysics, Part I: Lanthanide Pentafluorobenzoates

Highly luminescent, photostable, and soluble lanthanide pentafluorobenzoates have been synthesized and thoroughly characterized, with a focus on Eu(III) and Tb(III) complexes as visible emitters and Nd(III) , Er(III) , and Yb(III) complexes as infrared emitters. Investigation of the crystal structures of the complexes in powder form and as single crystals by using X-ray diffraction revealed five different structural types, including monomeric, dimeric, and polymeric. The local structure in different solutions was studied by using X-ray absorption spectroscopy. The photoluminescence quantum yields (PLQYs) of terbium and europium complexes were 39 and 15 %, respectively; the latter value was increased almost twice by using the heterometallic complex [Tb0.5 Eu0.5 (pfb)3 (H2 O)] (Hpfb=pentafluorobenzoic acid). Due to the effectively utilized sensitization strategy (pfb)(-) →Tb→Eu, a pure europium luminescence with a PLQY of 29 % was achieved.

X-ray absorption spectroscopic and magneto-chemical analysis of the atomic structure of copper(II) complexes with diacetyl monoxime 1′-phthalazinyl hydrazone

The atomic structure of copper(II) complexes based on diacetyl monoxime 1′-phthalazinyl hydrazone is studied by XANES spectral analysis and magnetochemistry. The XANES spectra at the CuK-edge are measured in C24H24N10Cu2O2 and C24H24N10Cu2O2 complexes. The calculations of the CuK-XANES spectra of the complexes in question are performed for a few structural models based on the full-potential finite difference method. By low-temperature magnetochemistry magnetic exchange parameters are determined, and a quantum chemical simulation of the exchange interaction is carried out within the broken symmetry approximation. Based on a combined analysis of the XANES spectra and magnetic exchange parameters, the most probable structural models of C24H24N10Cu2O2 and C24H24N10Cu2O2 complexes are found.

Binuclear metallochelates of 2-(N-tosylamino)benzal-2’-(hydroxymethyl)aniline: Syntheses, structures, and magnetic properties

Binuclear complexes of Co(II), Сu(II), and Pd(II) with 2-(N-tosylamino)benzal-2’-(hydroxymethyl)aniline are synthesized. The compositions and structures of the ligand and complexes are determined from the data of elemental analysis, IR spectroscopy, 1Н, 13С, and 15N NMR spectroscopy, X-ray absorption spectroscopy, and magnetochemical measurements in a temperature range of 294–77.4 K. All complexes are dimeric. The Cu…Cu and Cо…Cо distances equal to 3.03 and 2.99 Å, respectively, are obtained for the Cu(II) and Co(II) complexes. These complexes are characterized by the antiferromagnetic exchange interaction with 2J = –630 and –42 cm–1, respectively.

X-ray spectroscopy study of the chemical state of “invisible” Au in synthetic minerals in the Fe-As-S system

Abstract Minerals of the Fe-As-S system are the main components of Au ores in many hydrothermal deposits, including Carlin-type Au deposits, volcanogenic massive sulfide deposits, epithermal, mesothermal, sedimentary-hosted systems, and Archean Au lodes. The “invisible” (or refractory) form of Au is present in all types of hydrothermal ores and often predominates. Knowledge of the chemical state of “invisible” Au (local atomic environment/structural position, electronic structure, and oxidation state) is crucial for understanding the conditions of ore formation and necessary for the physical-chemical modeling of hydrothermal Au mineralization. In addition, it will help to improve the technologies of ore processing and Au extraction. Here we report an investigation of the chemical state of “invisible” Au in synthetic analogs of natural minerals (As-free pyrite FeS2, arsenopyrite FeAsS, and löllingite FeAs2). The compounds were synthesized by means of hydrothermal (pyrite) and salt flux techniques (in each case) and studied by X-ray absorption fine structure (XAFS) spectroscopy in a high-energy resolution fluorescence detection (HERFD) mode in combination with first-principles quantum chemical calculations. The content of “invisible” Au in the synthesized löllingite (800 ± 300 ppm) was much higher than that in arsenopyrite (23 ± 14 ppm). The lowest Au content was observed in zonal pyrite crystals synthesized in a salt flux. High “invisible” Au contents were observed in hydrothermal pyrite (40–90 ppm), which implies that this mineral can efficiently scavenge Au even in As-free systems. The Au content of the hydrothermal pyrite is independent of sulfur fugacity and probably corresponds to the maximum Au solubility at the experimental P-T parameters (450 °C, 1 kbar). It is shown that Au replaces Fe in the structures of löllingite, arsenopyrite, and hydrothermal pyrite. The Au-ligand distance increases by 0.14 Å (pyrite), 0.16 Å (löllingite), and 0.23 Å (As), 0.13 Å (S) (arsenopyrite) relative to the Fe-ligand distance in pure compounds. Distortions of the atomic structures are localized around Au atoms and disappear at R > ∼4 Å. Chemically bound Au occurs only in hydrothermal pyrite, whereas pyrite synthesized without hydrothermal fluid contains only Au°. The heating (metamorphism) of hydrothermal pyrite results in the decomposition of chemically bound Au and formation of Au° nuggets, which coarsen with increasing temperature. Depending on the chemical composition of the host mineral, Au can play a role of either a cation or an anion: the Bader atomic partial charge of Au decreases in the order pyrite (+0.4 e) > arsenopyrite (0) > löllingite (−0.4 e). Our results suggest that other noble metals (platinum group elements, Ag) can form a chemically bound refractory admixture in base metal sulfides/chalcogenides. The content of chemically bound noble metals can vary depending on the composition of the host mineral and ore history.

Synthesis and investigation of the structure of nanocomposites based on nickel nanoparticles dispersed in a phthalocyanine matrix

A method based on doping of pure nickel phthalocyanine (NiPc) with a polycrystalline potassium powder at relatively low temperatures (300°C) has been proposed for the synthesis of a magnetic nanocomposite containing nickel nanoparticles stabilized in the NiPc matrix. The structural analysis of the synthesized nanoparticles and changes in the NiPc initial matrix has been performed using X-ray diffraction, X-ray absorption spectroscopy, and transmission electron microscopy. It has been found that, at the doping level used in this study, the synthesized samples of the KxNiPc nanocomposites contain from 9 to 18% Ni in the form of metallic magnetic nanoparticles with an average size of more than 40 nm. It has been shown that the formation of nanoparticles is accompanied by a relative misorientation of persistent NiPc molecules with the unchanged structure of each of these molecules. The stabilization of nickel nanoparticles by the phthalocyanine matrix leads to the fact that the synthesized nanocomposites acquire time-conserving magnetic properties.

Local atomic structure of mono- and binuclear metal complexes based on 3-formylpyrone and 3-formylcoumarin bis-azomethines

A series of Cu, Ni, and Mn complexes based on formylpyrone and formylcoumarin azomethynes with 1,3- diaminepropanol-2. The analysis of XANES and EXAFS spectra of the Cu, Ni, and Mn complexes, which were processed by both Fourier and wavelet transforms, enables the determination of local atomic structural parameters and the unambiguous evidence of the formation of both dinuclear and mononuclear structures of these coordination compounds. The possibility of forming binuclear compounds is shown to depend mainly on the nature of the bridging ligand and be independent of the type of the polydentate azomethyne ligand: pyrone or coumarin. The obtained structural results are well consistent with the magnetochemical data for the complexes.

Determining the speciation of Zn in soils around the sediment ponds of chemical plants by XRD and XAFS spectroscopy and sequential extraction

For a correct assessment of risk of polluted soil, it is crucial to establish the speciation and mobility of the contaminants. The aim of this study was to investigate the speciation and transformation of Zn in strongly technogenically transformed contaminated Spolic Technosols for a long time in territory of sludge collectors by combining analytical techniques and synchrotron techniques. Sequential fractionation of Zn compounds in studied soils revealed increasing metal mobility. Phyllosilicates and Fe and Mn hydroxides were the main stabilizers of Zn mobility. A high degree of transformation was identified for the composition of the mineral phase in Spolic Technosols by X-ray powder diffraction. Technogenic phases (Zn-containing authigenic minerals) were revealed in Spolic Technosols samples through the analysis of their Zn K-edge EXAFS and XANES spectra. In one of the samples Zn local environment was formed by predominantly oxygen atoms, and in the other one mixed ZnS and ZnO bonding was found. Zn speciation in the studied technogenically transformed soils was due to the composition of pollutants contaminating the floodplain landscapes for a long time, and, second, this is the combination of physicochemical properties controlling the buffer properties of investigated soils. X-ray spectroscopic and X-ray powder diffraction analyses combined with sequential extraction assays is an effective tool to check the affinity of the soil components for heavy metal cations.

Ion implantation in nanodiamonds: size effect and energy dependence

Nanoparticles are ubiquitous in nature and are increasingly important for technology. They are subject to bombardment by ionizing radiation in a diverse range of environments. In particular, nanodiamonds represent a variety of nanoparticles of significant fundamental and applied interest. Here we present a combined experimental and computational study of the behaviour of nanodiamonds under irradiation by xenon ions. Unexpectedly, we observed a pronounced size effect on the radiation resistance of the nanodiamonds: particles larger than 8 nm behave similarly to macroscopic diamond (i.e. characterized by high radiation resistance) whereas smaller particles can be completely destroyed by a single impact from an ion in a defined energy range. This latter observation is explained by extreme heating of the nanodiamonds by the penetrating ion. The obtained results are not limited to nanodiamonds, making them of interest for several fields, putting constraints on processes for the controlled modification of nanodiamonds, on the survival of dust in astrophysical environments, and on the behaviour of actinides released from nuclear waste into the environment.