Thermal expansion of the one-dimensional conductor K2Pt(CN)4Br0.3·xH2O and K2Pt(CN)4·xH2O

Measurements of the thermal expansion coefficients of K₂Pt(CN)₄Br_0.3· xH₂O and K₂Pt(CN)₄·xH₂O show a large anisotropy of the a-and c- directions. Their temperature dependence could be described by a simple Grüneisen theory. In the range from 80–330°K no anomaly indicating a Kohn-Peierls transition could be found.     

Thermal analysis and brillouin scattering in CaPd(CN)4·5H2O: Possibility of a phase transition near - 70°C

A small peak of specific heat has been observed in CaPd(CN)₄·5H₂O at - 70°C by differential thermal analysis indicating the possibility of a phase transition at this temperature. This hypothesis seems to be confirmed by a Brillouin scattering investigation which shows that the six elastic stiffnesses c_ii, i = 1, …, 6 are affected near the same temperature. The results are compared to those which are available in other compounds containing the planar groups M(CN)₄^2?.     

Oscillator strengths from line absorption in a high-temperature furnace—II. The (0,0) band of the B2σ+—X2σ+ transition in CN*

Quantitative high-resolution absorption spectroscopy was applied to the (0,0) violet band of CN. The CN radical was prepared in a furnace at 1421°K containing pure cyanogen gas. Since the calculated CN concentration is dependent on the controversial CN heat of formation, only the relationship, f_υ = 6·84 X 10^-3exp (0·354δ), where f_υ is the excess over the initially assumed ΔH⁰_f(CN) = 100·8 kcal/mole, could be directly determined in this study with an estimated error in f_υ of ±20%. For δ = 0, our f_υ is a factor of 4·8 smaller than an average value of 0·033±0· derived from other measurements. If this latter value of f_υ is assumed, our relationship yields ΔH⁰_f(CN) = 105·3±1· kcal/mole or D₀(CN) = 7·66±0·05 eV. The rotational temperature and line widths for this band were also measured.     

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.     

Inelastic neutron scattering from the quasi-one-dimensional conductor K1.75[Pt(CN)4]·1.5H2O

Neutron inelastic scattering has been used to study the longitudinal and one of the transverse acoustic phonons, propagating along the [001]¹ direction in triclinic K_1.75[Pt(CN)₄]·1.5H₂O. This material appears to be a quasi-one-dimensional conductor, with a commensurate distortion. We observe a reasonably well defined Kohn anomaly, which shows little temperature dependence between 80 and 300 K.     

High pressure tuning of optical transitions in Mg[Pt(CN)4]·7H2O

Mg[Pt(CN)₄]·7H₂O belongs to the class of tetracyanoplatinates(II) which crystallize in columnar structures. In different M_x[Pt(CN)₄]·yH₂O (MCP) single crystals the in-chain Pt-Pt-distance R varies between 3.67 Å (NaCP) and 3.15 Å (MgCP). Two optical transitions can be observed in polarized emission with the electric field vector E either parallel or perpendicular to the columnar (c)-axis. Polarized emission spectra of MgCP are recorded under hydrostatic pressure up to p ≈ 18 kbar (at 295 K). The transition energy v?₆ can be tuned from 17,600 cm^-1 to about 12,000 cm^-1 (2.18-1.48 eV). The pressure induced red shift for the two transitions is: E 6 c: dv?₆/dp = -320±20 cm^-1/kbar, E ⊥ c: dv?_⊥/dp = -270±20 cm^-1/kbar. These values are discussed in the context of the known functional relationship (for ambient conditions) between v? and R.     

Structure of ZnZrF<Subscript>6</Subscript> · <Emphasis Type="Italic">n</Emphasis>H<Subscript>2</Subscript>O (<Emphasis Type="Italic">n</Emphasis> = 6–2) and ZnZrF<Subscript>6</Subscript> crystallohydrates according to vibrational spectroscopy data

Fluoridezirconate crystallohydrates ZnZrF₆ · nH₂O (n = 6–2) and anhydrous ZnZrF₆ are investigated by vibrational spectroscopy and thermography. The influence of the hydrate number on the structure of the cationic and anionic sublattices of the crystallohydrates is studied. The changes in the strength of HOH···F and HOH···O hydrogen bonds of coordinated and outer-sphere water molecules occurring with variations in the hydrate number are determined by changes in the IR spectra. The IR spectra of ZnZrF₆ · nH₂O (n =6, 4) compounds, which have isolated complex anions [ZrF₆]^2– in their structure, revealed a band with two peaks in the range of 3470–3430 cm^–1, which corresponds to stretching vibrations of coordinated water molecules. The spectra of ZnZrF₆ · nH₂O (n = 5, 3, 2, 1) crystallohydrates with a polymeric structure show a high-frequency shift of this band, which corresponds to weakening of hydrogen bonds. The vibrations of crystallization water molecules involved in the network of strong O–H···F and O–H···O hydrogen bonds manifest themselves in the spectra of ZnZrF₆ · nH₂O (n =5, 3) crystallohydrates by broad structureless bands in the region of stretching, bending, and libration vibrations.     

Raman spectroscopic study of the hydrogen and arsenate bonding environment in isostructural synthetic arsenates of the variscite group—M3+ AsO4·2H2O (M3+ = Fe,Al, In and Ga): implications for arsenic release in water

The Raman spectra of synthetic compounds equivalent to the variscite group: FeAsO₄·2H₂O AlAsO₄·2H₂O, GaAsO₄·2H₂O, and InAsO₄·2H₂O are reported. In particular, upon comparison of FeAsO₄·2H₂O to AlAsO₄·2H₂O, it is observed that the Type II (weak) H‐bond lengths in the latter are slightly longer, which is postulated to affect the stability (As release) in water at pH 5 and 7. Arsenate stretching and bending vibrations were found to be distinct in terms of spectral structure and therefore well suited for fingerprinting. The calculated As O bond strengths from existing crystallographic data showed no significant variations. The strongest ν₁ (AsO₄³⁻) stretch was used to monitor the As O bonding interactions in the four As O M units, where a shift of 114 cm⁻¹ was observed in the order FeAsO₄·2H₂O (lowest) < InAsO₄·2H₂O < GaAsO₄·2H₂O < AlAsO₄·2H₂O (highest); this order also followed exactly the measured arsenic release of these phases. This shift in ν₁ (AsO₄³⁻) position was rationalized to stem from the differences in the electronegativities of the M³⁺ cations. The trends mentioned above were verified and found to also hold for the isostructural phosphate analogues strengite (FePO₄·2H₂O) and variscite (AlPO₄·2H₂O) using published data. Therefore, it is postulated that, as observed with the stability of solution complexes, there may be a correlation between the electronegativity of the M³⁺ cation in these isostructural phases and their stability (As or P release) in water. Copyright © 2010 John Wiley & Sons, Ltd.     

Fluoreszenzlebensdauern einiger wasserhaltiger Salze des Europiums und des Terbiums

At 300°K the fluorescent lifetimes of the levels⁵D₀ of Eu³⁺ and⁵D₄ of Tb³⁺ were measured in the RE(C₂H₅SO₄)₃·9H₂O, RE(BrO₃)₃·9H₂O, RECl₃·6H₂O, RE(NO₃)₃·6H₂O and (RE)₂(SO₄)₃·8H₂O. The fluorescent lifetimes of the above mentioned hydrated crystals are preliminary determined by radiationless transitions. An empirical relation can be obtained for the probabilityw for the radiationless transitions of the formw=const·α _RE·α _Lattice. The factorsα _RE andα _Lattice depend only on the rare-earth ion or the lattice respectively. A structure of the interaction Hamiltonian between the rare-earth ion and the lattice is proposed, which leads to the empirically found relation. The influence of electron- andX-irradiation on the lifetime of the level⁵D₄ in TbCl₃·6H₂O was investigated at 77°K. A decrease of the lifetime and a nonexponential decay of the fluorescence were found. By heating up the crystal to room temperature thermoluminescence and annealing of the irradiation defects are observed.     

Rigid lattice NMR spectra of fast proton conductors H2Sb4O11-nH2O

Hydrated antimonic acids H₂Sb₄O₁₁ · 2H₂O and H₂Sb₄O₁₁ · 3H₂O are fast proton conductors with the same (Sb₄O₁₁)^2-covalent framework delimiting intercrossing channels. Using proton magnetic resonance in the very low temperature rigid-lattice regime we show that the channels of the structure are occupied by three species: oxonium ions (H₃O⁺), water molecules (H₂O) and hydroxylic protons (OH) attached to the framework. Quantitative analysis of the experimental spectra lead to a rewriting of the chemical formula, as (H₃O)_xSb₄O_11-y(OH)_y · zH₂O with x,y and z depending on the hydration state. Coexistence of oxonium ions and water molecules is compatible with the assumption of a Grotthuss-type mechanism for proton diffusion. Nuclear magnetic resonance of the completely dehydrated compound H₂Sb₄O₁₁ is also reported. The value of the second moment of the proton resonance line indicates that in this compound all the protons are attached to the (Sb₄O₁₁)^2- framework.     

Kinetic mechanisms of the uptake of atmospheric gases on the surface of sea salts. ClNO3 uptake on MgCl2 · 6H2O/NaCl

The uptake coefficients γ of chlorine nitrate on MgCl₂ · 6H₂O crystallites and a MgCl₂ · 6H₂O-NaCl mixture deposited from an aqueous solution are measured using a flow reactor with a movable salt-substrate-coated insert equipped in combination with a mass spectrometer at 295–428 K, [ClNO₃] = (0.2?12) × 10¹² cm^?3, and [H₂O] = 1.0 × 10¹² ? 4.3 × 10¹⁵ cm^?3. Immediately after the exposure of the salt substrate to a ClNO₃ flow, γ(t) decreases exponentially with time, γ(t) = γ₀ × exp(?t/τ) + γ _s , to a steady-state level, γ _s , which depends on the temperature and the ClNO₃ and H₂O concentrations. The main gas-phase product is Cl₂, HOCl appears only when water vapor is admitted into the reactor. The coefficient of steady-state uptake on wetted MgCl₂ · 6H₂O at 295 K can be described by the approximation γ = a + b [H₂O] with a = 3.5 × 10^?3 cm³ and b = 3.2 × 10^?18 cm³. The mechanism of the uptake of ClNO₃ on MgCl₂ · 6H₂O is discussed. The experimental data are treated within the framework of a steady-state uptake model to estimate the heat of adsorption of ClNO₃ on MgCl₂ · 6H₂O (Q _ad = 62 kJ/mol) and the activation energy of the bimolecular heterogeneous reaction ClNO₃ + Z _s = 2Cl₂ + Mg(NO₃)₂ · 6H₂O (E _a = 21.8 kJ/mol; Z _s denotes a ClNO₃-MgCl₂ · 6H₂O surface complex). When the MgCl₂ · 6H₂O: NaCl is varied from 0 to ～3 wt %, the steady-state uptake coefficient changes from the value corresponding to uptake on pure NaCl to that characteristic of uptake on pure MgCl₂ · 6H₂O.     

Magnetic properties of uranium hexacyanomanganate

A Prussian blue type compound of the stoichiometric composition U^IV[Mn^II(CN)₆]·5H₂O has been prepared. It has been shown that the compound exhibits ferrimagnetism with a Curie temperature T_c=36.8 K.     

Electrical conduction studies on one-dimensional Cs2[Pt(CN)4](FHF)0.39 and Rb2[Pt(CN)4](FHF)0.40

Variable temperature (300-40 K) 4-probe d.c. conduction studies on Cs₂[Pt(CN)₄](FHF)_0.39 and Rb₂[Pt(CN)₄](FHF)_0.40 are described. In these salts T_3D occurs at a lower temperature than in K₂[Pt(CN)₄]Br_0.3·3H₂O and this is attributed to the absence of an inter-chain network of hydrogen bonded water molecules in the bifluorides.     

An ESR study of phase transitions in crystals of M(BF4)2·6H2O (M = Fe,Co, Ni,Zn)

From a temperature dependent ESR study of Mn²⁺-doped crystals of M(BF₄)₂·6H₂O, M Zn, Co and Ni, new structural phase transitions have been detected and studied. First order structural phase transitions occur in Co(BF₄)₂·6H₂O at T₁ ~ 281K, T₂~189 K and T₃~172K (during cooling), in Zn(BF₄)₂·6H₂O at T₁ ~ 286 K and in Ni(BF₄)₂·6H₂O at T₁ ~ 301 K. A continuous phase transition occurs in Co(BF₄)₂·6H₂O at T_p ~ 257 K, in Zn(BF₄)₂·6H₂O at T_p ~ 277 K and in Ni(BF₄)₂·6H₂O at T_p ~ 294 K. The ESR spectral characteristics suggest similarities in the structures of these fluoroborate compounds in the phase above T₁ with the room temperature structure of Mg(ClO₄)₂·6H₂O. All these compounds are found to have a tendency to crystallise in a triply-twinned pseudo-hexagonal form, although the unit cell above T₁ is found to be orthorhombic. The structural changes related to the water octahedron around the metal at T₁ were found to be very small and basically the same for these three compounds. Although the unit cell structure of Fe(BF₄)₂·6H₂O above the first order phase transition temperature T₁ was found to be similar to that of the other fluoroborate compounds, the structural changes occurring at T₁ appeared to be quite different. The low temperature thermal behaviour differs considerably in the Co, Fe and Zn compounds.     

Magnetic and Mössbauer studies of cyanide-bridged bimetallic assembly [Mn(cyclam)][Fe(CN)6]·3H2O

Cyanide-bridged bimetallic assembly [Mn(cyclam)][Fe(CN)₆]·3H₂O (cyclam=1,4,8,11-tetraazacyclotetradecane) was synthesized from the reaction of trans-[MnCl₂(cyclam)]Cl with K₃Fe(CN)₆. A linear chain structure consisting of alternating [Mn(cyclam)]³⁺ and [Fe(CN)₆]³⁻ units was indicated by the IR and Mössbauer spectra. The variable-temperature magnetization and Mössbauer measurements revealed that this complex exhibited a long-range ordering below 6.8 K. The magnetic behavior of the complex was based on intrachain ferromagnetic and interchain antiferromagnetic interactions.     

X-ray K-absorption studies ofsome ruthenium compounds

X-ray K-absorption studies of ruthenium in ruthenium metal,RuO₂, K₂(RuCl₆) and K₄[Ru(CN)₆]: 3H₂O have been carried out using 400 mm bent crystal (mica) spectrograph. K-absorption edge of ruthenium in these compounds lies on the higher energy side with respect to that in the ruthenium metal; the divalent K₄[Ru(CN)₆]·3H₂O gives the shift in the range of tetravalent compounds RuO₂ and K₂[RuCl₆]. This discrepancy has been explained on the basis of molecular orbital picture.     

Time-filtering effect in the Mössbauer spectrum

Details of the delayed-coincidence transmission Mössbauer spectra have been observed using a ⁵⁷Co source in copper and a single-line absorber K₄Fe(CN)₆·3H₂O, for fairly narrow predetermined delayed time intervals. A very good agreement was found between the experimental results and theoretical predictions.     

The influence of PEO on the synthesis and electrochemical properties of VO2 and V3O7·nH2O nanobelts as a cathode for lithium battery

In this paper, we report the hydrothermal synthesis of VO₂, poly(ethylene oxide) (PEO)/VO₂,V₃O₇·nH₂O and PEO/V₃O₇·nH₂O nanobelts by using 1,2-propylene carbonate (1,2-PC (C₄H₆O₃)) and poly(ethylene glycol) (PEG) as templates, respectively. Structure and morphology of the samples were investigated by XRD, FTIR, SEM, and TEM. The vanadium oxide (VO₂) nanobeltcomposite show the initial specific capacity 152?mA?h?g^?1, whereas PEO/VO₂ shows 182?mA?h?g^?1. The pure V₃O₇·nH₂O nanobelts shows the initial specific capacity 192?mA?h?g^?1, while PEO/V₃O₇·nH₂O nanobelts show 297?mA?h?g^?1. It was found that PEO/VO₂ and PEO/V₃O₇·nH₂O nanocomposites show better cyclic performance and high discharge stability compared to pure vanadium oxide nanomaterials. The role of the polymeric PEO component of the hybrid material seems to be the stabilization and improvement of the specific capacity due to probable homogeneous distribution between the nanobelts. The TEM images indicate that PEO works as a surfactant to decrease the dimensions of nanobelts.     

Influence of hydrostatic pressure on the plasma reflection edge of K2Pt(CN)4Br0.3 · 3H2O

A blue shift of the optical plasma reflection edge of the one-dimensional metal K₂Pt(CN)₄Br_0.3 · 3H₂O under hydrostatic pressures up to 7.2 katm has been observed. The shift (75 cm^?1katm^?1±30%) is interpreted as an increase of the plasma frequency and is correlated with the changes in the interatomic distances under pressure.