Vibrational analysis of the H4I2O102− ion in CuH4I2O10·6H2O

Vibrational wavenumbers (IR and Raman) have been calculated for the diperiodate ion H₄I₂O₁₀²⁻ on the basis of a DFT method and assigned to experimental wavenumbers obtained from CuH₄I₂O₁₀·6H₂O. To obtain vibrational wavenumbers in the range comparable to the experiment it was necessary to use the complex [(H₄I₂O₁₀)₇(Cu(H₂O)₆)₆]²⁻. Smaller complexes lead to much too high wavenumbers for the O‐H stretching vibrations and to too small wavenumbers in the range of the internal vibrations of the anion. On the basis of the results of the calculations an assignment of the Raman lines observed for CuH₄I₂O₁₀· 6H₂O to the vibrational modes is given. Copyright © 2008 John Wiley & Sons, Ltd.     

Exchange interactions and spin dynamics in a [CuNd2(C4O4)4(H2O)16]·2H2O crystal

Crystalline [CuNd₂(C₄O₄)₄(H₂O)₁₆]·2H₂O constructed of complexes of trivalent neodymium and divalent copper, has been synthesized and studied by EPR. The square anion groups (C₄O₄) enter as bridge ligands, forming chains of neodymium ions interconnected by (C₄O₄)Cu(C₄O₄) fragments. It is found that the relaxation rate of the neodymium subsystem at room temperature significantly exceeds the exchange interaction rate between copper and neodymium ions. Under these conditions the magnetic properties of the crystal are determined by two magnetically nonequivalent chains of copper ions, which do not interact. The intrachain exchange interaction via hydrogen bonds is estimated to be ∼0.1 cm⁻¹. As one proceeds from the high-temperature (250<T<300 K) to the low-temperature region (T<40 K), a substantial change in the nature of the interaction is revealed. An unusual magnetic structure given in a crystal is observed at low temperatures, which is determined by the presence of two magnetically nonequivalent “ribbons,” formed by the interacting copper and neodymium ions: chains of copper ions are framed on two sides by chains of neodymium ions. The magnitude of the parameter of the exchange interaction between the copper and neodymium ions is estimated as J ^Cu-Nd⩾0.2 cm⁻¹. An exchange interaction between magnetically nonequivalent neodymium ions is not revealed in the EPR spectra. Fiz. Tverd. Tela (St. Petersburg) 39, 2057–2061 (November 1997)     

Raman spectroscopic study of the uranyl sulphate mineral jáchymovite (UO2)8(SO4)(OH)14· 13H2O

Raman spectra of jáchymovite, (UO₂)₈(SO₄)(OH)₁₄·13H₂O, were studied, complemented with infrared spectra, and compared with published Raman and infrared spectra of uranopilite, [(UO₂)₆(SO₄)O₂(OH)₆(H₂O)₆]·6H₂O. Bands related to the stretching and bending vibrations of (UO₂)²⁺, (SO₄)²⁻, (OH)⁻ and water molecules were assigned. U O bond lengths in uranyl and O H· · ·O hydrogen bond lengths were calculated from the Raman and infrared spectra. Copyright © 2009 John Wiley & Sons, Ltd.     

Phase transitions in a metal–organic coordination polymer: [Zn2(C8H4O4)2(C6H12N2)] with guest molecules. Thermal effects and molecular mobility

Thermal effects of a series of [Zn₂(C₈H₄O₄)₂(C₆H₁₂N₂)] porous compound with the guest molecules located in the pores were studied using differential scanning calorimetry combined with solid-state ¹H nuclear magnetic resonance spectroscopy. The intercalation of the molecules was shown to produce various thermal anomalies and phase transitions, which were characterized and analyzed.     

Crystal structure of di-(L-serine) phosphate monohydrate [C3O3NH7]2H3PO4H2O

The crystal structure of di-(L-serine) phosphate monohydrate [C₃O₃NH₇]₂H₃PO₄H₂O is determined by single-crystal x-ray diffraction. The intensities of x-ray reflections are measured at temperatures of 295 and 203 K. The crystal structure is refined using two sets of intensities. It is established that, in the structure, symmetrically nonequivalent molecules of L-serine occur in two forms, namely, the monoprotonated positively charged molecule CH₂(OH)CH(NH₃)⁺COOH and the zwitterion CH₂(OH)CH(NH₃)⁺COO^?, which are linked with each other and with the H₂PO ^?₄ ion through a hydrogen-bond system involving water molecules.

     

草酸铕颗粒微米层状颗粒的合成及其光学性能

在室温条件下, 以柠檬酸钠为辅助剂, 通过简单沉淀法合成了草酸铕Eu₂(C₂O₄)₃·10H₂O微米层状颗粒. 应用X射线衍射、X射线电子能谱、场发射扫描电子显微镜、光致发光光谱对Eu₂(C₂O₄)₃·10H₂O结构与性能进行了表征. 讨论了草酸铕微米层状颗粒可能的形成机理.     

The absorption cross sections of N2, O2, CO,NO, CO2, N2O,CH4, C2H4, C2H6 and C4H10 from 180 to 700Å

The absorption cross sections of N₂, O₂, CO, NO, CO₂, N₂O, CH₄, C₂H₄, C₂H₆, C₄H₁₀ have been measured photoelectrically in the 180–700 Å region using synchrotron radiation. The absorption cross sections in the region λ ≥ 500 Å was found to be structureless and to increase monotonically with wavelength for all gases. The positions of the structure observed in the 520–720 Å region for N₂, O₂, CO₂ and N₂O are consistent with the various Rydberg series reported by previous authors.     

O,O′-Dimethyl diphenyldithiophosphates of titanium(IV): synthesis,spectroscopic, DFT and biological studies

Dimethyl diphenyldithiophosphate complexes of titanium(IV), [(C₅H₅)₂Ti{S₂P(OAr)₂}_nCl_2-n] (Ar?= 2,4-(CH₃)C₆H₃, 2,5-(CH₃)C₆H₃, 3,4-(CH₃)C₆H_3, 3,5-(CH₃)C₆H_3, 3-CH₃-4-Cl-C₆H₃O; n?=?1 and 2) have been synthesised and characterised by various physicochemical techniques along with computational analysis of the complexes (2), (9) and (10) using density functional theory (DFT) and time-dependent DFT (TDDFT). Comparison of antimicrobial activity of the free ligands and complexes has shown that the complexes are more effective than the free ligands. The in vitro cytotoxic by using a MTT staining method with RAW 264.7 cells (mouse macrophages) have been investigated. On the basis of analytical and DFT data, a distorted trigonal bipyramidal around titanium(IV) may be assigned to the complexes (1–5) and distorted octahedral geometries for the complexes (6–10).     

Raman spectroscopic study of the arsenite mineral vajdakite [(Mo6+O2)2(H2O)2As3+2O5]·H2O

Raman spectra of vajdakite, [(Mo⁶⁺O₂)₂(H₂O)₂As O₅]·H₂O, were studied and interpreted in terms of the structure of the mineral. The Raman spectra were compared with the published infrared spectrum of vajdakite. The presence of dimolybdenyl and diarsenite units and of hydrogen bonded water molecules was inferred from the Raman spectra which supported the known and published crystal structure of vajdakite. Mo O and O H···O bond lengths were calculated from the Raman spectra. Copyright © 2009 John Wiley & Sons, Ltd.     

Thermal ion-molecule reactions in oxygen-containing molecules. Condensation-elimination reactions involving CH3+ and C2H4O+ in acetaldehyde and ethylene oxide

The condensation-elimination reactions involving CH₃⁺ and C₂H₄O⁺ in acetaldehyde and ethylene oxide have been studied using a time-of-flight mass spectrometer. The CH₃⁺ ions react with acetaldehyde and ethylene oxide to form C₂H₃⁺, C₂H₄⁺, C₂H₅⁺ and CH₃O⁺. Further studies in the reactions of CH₃⁺ were made in methane-acetaldehyde (or ethylene oxide) mixtures, and the formation mechanism of C₂H₅⁺ and CH₃O⁺ was elucidated. The C₂H₄O⁺ ions react with acetaldehyde and ethylene oxide to form C₃H₅O⁺, C₃H₆O⁺, and C₃H₇O⁺. Mechanistic studies in the ionic reactions involving the isomeric ions (CH₃CHO⁺ and CH₂CH₂O⁺) was also made in acetaldehyde-d₄-ethylene oxide mixtures. From the distribution of isotopic product ions, the structures of the product ions and the condensation-elimination reaction mechanism were examined. In addition, the rate constants for the product ions were obtained.     

氯化苯并咪唑镧的荧光光谱

对新合成的化合物氯化苯并咪唑镧HCl₄·[C₇H₆N₂(H₂O)₂]₂La及其LaCl₃·5H₂O的水溶液进行了三维荧光光谱测定,讨论了HCl₄·[C₇H₆N₂(H₂O)₂]₂La在不同波长的光激发下的荧光特性,荧光强度与浓度的关系及标题化合物的上转换荧光,即在540nm绿光的激发下可以获得紫外光(290nm)和近紫外光(360nm).     

Magnetic domain behaviour of MgFe2O4-CoFe2O4 system

Ferrites with the composition Mg_1−x CO _x Fe₂O₄(0<x≤0·33) were synthesized by solid state reaction between MgO,α-Fe₂O₃ and CoFe₂O₄ at 1300°C. The compounds were analyzed from the results of x-ray diffraction, magnetic hysteresis and initial susceptibility (χ) studies. All the compounds of the series were found to be monophasic with no appreciable change in their lattice parameter. The saturation magnetization and coercive field (H _c ) values increased with increasing cobalt ferrite content. Similarly, the shapes of theχ-T curves and temperature variations ofH _c values indicated that the magnetic behaviour changes from multi-domain to single domain with increasing cobalt content. The results are similar to those observed for the (MgFe₂O₄)_1−x (Co₃O₄) system.     

The infrared spectra of tutton salts 1. A comparative study of (NH4)2 M″(SO4)2·6H2O (M″=Ni,Co or Mg)

The infrared spectra of (NH₄)₂M″(SO₄)₂.6H₂O has been analysed in the region 4000–250 cm⁻¹. The dynamics of each crystal has been discussed in terms of 234 phonon modes, including 3 acoustical ones, using the unit cell approximation. The ambiguity in the assignments of the bands in the region 900–500 cm⁻¹ has been removed by assigning the bands in this region to the libratory modes of H₂O molecules. It has been concluded that the NH ₄ ⁺ and SO ₄ ²⁻ ions have a symmetry lower thanT _dand also the complex [M″(H₂O)₆]²⁺ has a symmetry lower than O _h . The hydrogen bonding is the strongest in the Ni-salt and the weakest in the Mg-salt.     

Oxide ion conduction in Nd9.33(SiO4)6O2 and Sr2Nd8(SiO4)6O2 single crystals grown by floating zone method

Single crystals of Nd_9.33(SiO₄)₆O₂ and Sr₂Nd₈(SiO₄)₆O₂ oxide ion conductors with the oxyapatite structure were grown without any macroscopic defect by the floating zone method. The oxide ion conductivity of the Sr₂Nd₈(SiO₄)₆O₂ single crystal varied with the distance from its seed crystal along the growth direction, because of its changing deficiency in Sr content. Its stoichiometric portion had a lower electrical conductivity by about five orders of magnitude at 600 °C than the value for Nd_9.33(SiO₄)₆O₂ single crystal. Structural refinement of neutron diffraction data for powdered Nd_9.33(SiO₄)₆O₂ single crystal showed that the previous structure analysis was misleading. Cation vacancies were present only at 4f site and its channel oxygen site was fully occupied in space group of P6₃/m. The oxygen had an anisotropic displacement along the channel in the refined oxyapatite structure.     

Formation mechanisms and crystallographic characteristics of metastable VO2(A) nanofiber hydrothermally synthesised in V2O5–H2C2O4–H2O system

There are many similarities between VO₂(B) and VO₂(A) from crystallographic view. However, missing of VO₂(A) during the preparation of VO₂ polymorph confused many researchers. Here, the preparation of VO₂(A) was studied systemically via a hydrothermal method in V₂O₅–H₂C₂O₄–H₂O system. As a metastable phase, it can be transferred from VO₂(B) by assembling process. Usually, poly-crystal VO₂(A) nano-fibers are formed by this process. On contrast, owing to the small energy gap between meta-stable VO₂(A) and stable VO₂(R), single crystal VO₂(A) with regular shape can also be obtained by exfoliating some parts of VO₂(R) during non-equilibrium cooling process. VO₂(A) has higher phase transition temperature than stable VO₂(R). The hysteresis in this phase transition can be observed by DSC measurement and the phase transition temperature of VO₂(A) can be tuned down by tungsten doping.     

Vibrational analysis of NaM2OH(H2O)(MoO4)2/D2O [M=Ni,Zn]

The infrared and Raman spectra of NaNi₂OH(H₂O)(MoO₄)₂ and NaZn₂OH (H₂O)(MoO₄)₂ and their partially deuterated analogues are recorded and analysed on the basis of vibrations of MoO ₄ ²⁻ tetrahedra and H₂O molecules. The MoO ₄ ²⁻ groups are found to be more distorted in NaNi₂OH(H₂O)(MoO₄)₂ than in the other compound. Bands indicating the presence of H₃O⁺ ions are not observed in NaZn₂OH(H₂O)(MoO₄)₂ ruling out the possibility of the formulation of NaZn₂OHO(MoO₃OH)₂. Hydrogen bonds of medium strength are present in both the compounds.     

Structural transformations in LiGd9(SiO4)6O2 and Ca2Gd8(SiO4)6O2 crystals containing isolated [SiO4] complexes: Raman spectroscopic study

The vibrational spectra of single crystals of the LiGd₉(SiO₄)₆O₂ and Ca₂Gd₈(SiO₄)₆O₂ oxyapatites have been studied using Raman spectroscopy at room and high temperatures. The spectra of internal and external vibrations in these structures have been resolved. The structural transformation of the LiGd₉(SiO₄)₆O₂ and Ca₂Gd₈(SiO₄)₆O₂ oxyapatites in the processes of melting and crystallization, as well as during rapid quenching of the melt, has been investigated. It has been found that the melting of the LiGd₉(SiO₄)₆O₂ compound has an incongruent character and that new metastable disordered phases are formed during rapid quenching of the Ca₂Gd₈(SiO₄)₆O₂ melt.     

Protonic conductivity and lithium intercalation in a new iron hydroxyphosphate hydrate: (H3O)[Fe(H2O)]3[H8(PO4)6]·3H2O

A new hydroxonium iron phosphate, (H₃O)[Fe(H₂O)]₃[H₈(PO₄)₆]·3H₂O, was synthesized through a precipitation route by means of acidic media. The crystal structure was solved by X-ray powder diffraction. Electrochemical characterizations, performed on this compound, show reversible intercalation of lithium and substantial lithium diffusion. Protonic conductivity is observed in agreement with the simultaneous presence of H₂O, hydrated protons and OH groups in the large intersecting tunnels of this intersecting tunnel structure.     

Studies on partially oxidised one-dimensional bis(oxalato)platinate salts containing divalent cations

The preparation and electrical conduction properties of the isostructural one-dimensional conductors Ni_0.84[Pt(C₂O₄)₂]·6H₂O(Ni-OP) and Mn_0.81[Pt(C₂O₄)₂]·6H₂O(Mn-OP) are described. Ni-OP exhibits a similar tem dependence of conductivity to the isostructural compounds Co_0.83[Pt(C₂O₄)₂]·6H₂O(Co-OP) and Zn_0.81[Pt(C₂O₄)₂]·6H₂O whereas the behaviour of Mn-OP is rather like that of K₂[Pt(CN)₄]Br_0.3·3H₂O. These differences are discussed in terms of the variation from compound to compound of the critical temperature for the formation of the “non-Peierls” superstructure (T_c) and the temperature at which the CDW/PD on adjacent conducting chains undergo three-dimensional ordering (T_3D). The variation of thermopower with temperature for Co-OP and Mg_0.82[Pt(C₂O₄)₂]·6H₂O is reported and related to the conduction properties and phase changes which have been observed for these compounds. For the isostructural series M_0.8[Pt(C₂O₄)₂]·6H₂O (M = Mg, Mn, Co, Ni or Zn) the variation of (T_3D) from compound to compound is related to differences in the polarizing power of the cations.