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61.
S. B. Artemkina N. G. Naumov A. V. Virovets V. E. Fedorov 《Russian Journal of Coordination Chemistry》2013,39(1):1-5
A solid solution Mo6 ? x Nb x I11 (x = 1.1–1.5) containing cluster cores {Mo5NbI8} is obtained by the high-temperature reaction of molybdenum, niobium, and iodine (550°C, 70 h, quartz ampule). According to the X-ray diffraction data, heating at 800°C in a molybdenum container results in the decomposition of the solution to Mo6I12 and Nb6I11. According to the X-ray structure analysis data, the compounds are isostructural to the high-spin modification Nb6I11 (space group Pccn). The presence of Nb atoms in the structure changes the structural type from the layered (Mo6I12) to framework structure, noticeably increases the metalmetal distances (2.661–2.716 Å, 2.695 Å) Mo6 octahedron with the retention of the distance from the metal (M) to the μ3-“capped” I atoms, and strongly elongates the M6-I-M6 bridges almost to the value observed in Nb6I11. 相似文献
62.
Dr. Antoine Demont Dr. Carmelo Prestipino Dr. Olivier Hernandez Dr. Erik Elkaïm Serge Paofai Prof. Nikolaï Naumov Dr. Bruno Fontaine Prof. Régis Gautier Dr. Stéphane Cordier 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(38):12711-12719
The crystal structure of Cs2BaTa6Br15O3 has been elucidated by using synchrotron X‐ray powder diffraction and absorption experiments. It is built from edge‐bridged octahedral [(Ta6${{\rm Br}{{{\rm i}\hfill \atop 9\hfill}}}$ ${{\rm O}{{{\rm i}\hfill \atop 3\hfill}}}$ )${{\rm Br}{{{\rm a}\hfill \atop 6\hfill}}}$ ]4? cluster units with a singular poor metallic electron (ME) count equal to thirteen. This leads to a paramagnetic behaviour related to one unpaired electron. The arrangement of the Ta6 clusters is similar to that of Cs2LaTa6Br15O3 exhibiting 14‐MEs per [(Ta6${{\rm Br}{{{\rm i}\hfill \atop 9\hfill}}}$ ${{\rm O}{{{\rm i}\hfill \atop 3\hfill}}}$ )${{\rm Br}{{{\rm a}\hfill \atop 6\hfill}}}$ ]5? motif. The poorer electron‐count cluster presents longer metal–metal distances as foreseen according to the electronic structure of edge‐bridged hexanuclear cluster. Density functional theory (DFT) calculations on molecular models were used to rationalise the structural properties of 13‐ and 14‐ME clusters. Periodic DFT calculations demonstrate that the electronic structure of these solid‐state compounds is related to those of the discrete octahedral units. Oxygen–barium interactions seem to prevent the geometry of the octahedral cluster to strongly distort, allowing stabilisation of this unprecedented electron‐poor Ta6 cluster in the solid state. 相似文献
63.
N. I. Solin L. N. Romashev S. V. Naumov A. A. Saranin A. V. Zotov D. A. Olyanich V. G. Kotlyar O. A. Utas 《Technical Physics》2016,61(2):233-239
We consider methods for controlling magnetoresistive parameters of magnetic metal superlattices, manganites, and magnetic semiconductors. By reducing the thickness of ferromagnetic layers in superlattices (e.g., Fe layers in Fe/Cr superlattices), it is possible to form superparamagnetic clustered–layered nanostructures with a magnetoresistance weakly depending on the direction of the external magnetic field, which is very important for applications of such type of materials. Producing Mn vacancies and additionally annealing lanthanum manganites in the oxygen atmosphere, it is possible to increase their magnetoresistance by more than four orders of magnitude. By changing the thickness of p–n junction in the structure of ferromagnetic semiconductors, their magnetoresistance can be increased by 2–3 orders of magnitude. 相似文献
64.
Absolute rate constants for hydroxyl radical, azide radical, and hydrated electron reactions with a sulfa drug 4,4'‐diamino diphenyl sulfone (dapsone) in water have been evaluated using electron pulse radiolysis technique. Absolute rate constants for hydroxyl radical and azide radical were determined as (8.4 ± 0.3) × 109 and (5.6 ± 0.5) × 109 M?1 s?1, respectively. The reduction of dapsone with the hydrated electron occurred with rate constant of (9.2 ± 0.1) × 109 M?1 s?1. Hydroxyl radical reactions result in the synchronous formation of adduct as well as anilino radical. The interesting observation is that the yield of the anilino radical increases with increase in pH. Contrary to this, the yield of the adduct decreases with pH. We propose that hydroxyl radical adds predominantly to the aniline. In contrast, the reaction of azide radical with the dapsone suggests that the reaction occurs at the –NH2 moiety of the aniline ring. The free radical electron transfer from dapsone to parent radical cation of non‐polar solvent also results in the formation of anilino radical only suggesting that the radical cation of dapsone has a short lifetime. The reaction of hydrated electrons with the dapsone suggests that the reaction occurs at different reaction site. The experimental results supported by theoretical calculations of this study provide fundamental mechanistic parameters that probably decide the fate of the radical cation of aniline derivatives. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
65.
66.
Abeer F. Shunnar Dr. Bhausaheb Dhokale Dr. Durga Prasad Karothu David H. Bowskill Dr. Isaac J. Sugden Dr. Hector H. Hernandez Prof. Panče Naumov Dr. Sharmarke Mohamed 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(21):4752-4765
The discovery of molecular ionic cocrystals (ICCs) of active pharmaceutical ingredients (APIs) widens the opportunities for optimizing the physicochemical properties of APIs whilst facilitating the delivery of multiple therapeutic agents. However, ICCs are often observed serendipitously in crystallization screens and the factors dictating their crystallization are poorly understood. We demonstrate here that mechanochemical ball milling is a versatile technique for the reproducible synthesis of ternary molecular ICCs in less than 30 min of grinding with or without solvent. Computational crystal structure prediction (CSP) calculations have been performed on ternary molecular ICCs for the first time and the observed crystal structures of all the ICCs were correctly predicted. Periodic dispersion-corrected DFT calculations revealed that all the ICCs are thermodynamically stable (mean stabilization energy=−2 kJ mol−1) relative to the crystallization of a physical mixture of the binary salt and acid. The results suggest that a combined mechanosynthesis and CSP approach could be used to target the synthesis of higher-order molecular ICCs with functional properties. 相似文献
67.
I. A. Litvinov O. N. Kataeva L. V. Ermolaeva G. A. Vagina T. V. Troepol'skaya V. A. Naumov 《Russian Chemical Bulletin》1991,40(1):62-67
Aroyl- and acetylhydrazones of acet- (I) and benzaldehydes (IV) and benzoylhydrazones of acet- (II) and benzaldehydes (III) were studied by x-ray structural and quantum-chemical methods in order to establish their structures. Compund (I) was the EEZ structure in the crystal. Calculations and spectral data showed that the EEE form occurs in nonpolar solvents and in the gas phase. According to crystallographic data molecules (I)–(IV) are the E-isomers (relative to the N-N bond) and the hydrazone fragments are planar. Intermolecular N-H...O H-bonds from in the crystals. The data obtained suggest that the majority of acylhydrazones are conformationally rigid on dissolution although exceptions do occur. Apparently the reasons for the difference of acetyl- and benzoylhydrazones in electrocarboxylation reactions are electronic and not steric factors.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 75–81, January, 1991. 相似文献
68.
Maria S. Tarasenko Nikolay G. Naumov Dmitry Yu. Naumov Sung-Jin Kim Vladimir E. Fedorov 《Polyhedron》2008
A series of new compounds containing rare earth cations (Eu to Yb) and paramagnetic cluster anion [Re6Te8(CN)6]3− was prepared and investigated. The X-ray structural analyses have revealed that the compounds [{Ln(H2O)4}{Re6Te8(CN)6}] · 2.5H2O; Ln = Eu (1), Tb (3), Dy (4), Ho (5), Er (6), Tm (7), [{Gd(H2O)3}{Re6Te8(CN)6}] · 2.5H2O (2) and [{Yb(H2O)4}{Re6Te8(CN)6}] (8) are three-dimensional polymers based on Re–CN–Ln interactions. Measurements of magnetic susceptibility for 2 and 5 showed that effective magnetic moment (at 300 K) was 8.13 μB for compound 2 and 10.79 μB for compound 5 with weak antiferromagnetic ordering appeared at low temperatures. 相似文献
69.
Goloshumova A. A. Tarasova A. Yu. Isaenko L. I. Yelisseyev A. P. Shubin Yu. V. Naumov D. Yu. 《Crystallography Reports》2018,63(6):1022-1026
Crystallography Reports - A new compound, SrPb3Br8, has been synthesized and investigated by X-ray diffraction and spectroscopic methods. Its crystal structure is described as follows: Pnma, a =... 相似文献
70.
A.V. Gurevich G.G. Mitko V.P. Antonova A.P. Chubenko A.N. Karashtin S.V. Kryukov A.S. Naumov L.V. Pavljuchenko M.O. Ptitsyn V.A. Ryabov S.Ya. Shalamova A.L. Shepetov Yu.V. Shlyugaev L.I. Vildanova K.P. Zybin 《Physics letters. A》2009,373(39):3550-3553
The observational evidence of RB-EAS discharge in a thunderstorm atmosphere is presented. After RB-EAS discharge we name a discharge of a special type developing due to the runaway breakdown (RB) mechanism while an extensive atmosphere shower (EAS) passes through a thundercloud electric field. The observations were fulfilled at the Tien-Shan Mountain Cosmic Ray Station. The widely spread system of oscillation detectors, the special EAS trigger array and the HF radio interferometer were used for measurements. 相似文献