Structural chemistry and magnetism of dicyclopentadienidehalides of lanthanides Part 8: terbiumdicyclopentadienidebromide [Tb(C5H5)2Br]2

A single-crystal X-ray structural investigation of [Tb(C₅H₅)₂Br]₂ revealed the [Sc(C₅H₅)₂Cl]₂-type structure, space group P2₁/c, with a = 1407.6(2) pm, b = 1644.7(2) pm, c = 1370.6(9) pm, β = 93.46(3)°, V = 3167(2) × 10⁶ pm³, D_c = 2.322 g cm⁻³ and Z = 6 dimers (R = 0.036 for 4627 reflections with I > 3σ(I)). The metal centres have the pseudosymmetry C_2v. Magnetic susceptibility data show Curie-Weiss behaviour between 213 and 6 K with θ_p = −4.5(3) K and a magnetic moment μ = 9.8(1) μ_B close to the Tb³⁺ free-ion value (9.72 μ_B). Below 6 K, deviations from Curie-Weiss behaviour are observed, and at 5.3 K a maximum in the susceptibility is detected which may be caused by intradimer antiferromagnetic spin coupling. The magnetic properties are compared with the prediction of various models, starting from cubic crystal fields and isotropic intramolecular exchange interactions, followed by extension to lower crystal field symmetry (orthorhombic) and anisotropic contributions to the spin coupling. However, a reasonable agreement between the measured and calculated data was not obtained. As in [Gd(C₅H₅)₂Br]₂, the low-temperature behaviour is governed by effects which cannot be described by spin coupling models in the generally accepted form.     

Novel BEDT-TTF salts with magnetic anions [MoOCl4(H2O)] and [Re2(NCS)10]

We report two novel BEDT-TTF salts containing magnetic transition metal anions. Both compounds are unusual in not containing discrete layers of anions and cations. In (BEDT-TTF)[MoOCl₄(H₂O)] the anions form hydrogen-bonded chains that lie in between 1-dimensional ribbons of edge-linked BEDT-TTF molecules. The compound is semiconducting with σ₃00K 0.5Scm^{− 1} E_A0.leV. In (BEDT-TTF)₃[Re₂(NCS)₁₀] CH₂Cl₂ no continuous network of BEDT-TTF exists, however π-π interactions are seen between the cation and the [Re₂(NCS)₁₀]^{3 −} anion. The compound is semiconducting with σ300K 0.01Scm⁻¹; E_A = 0.30eV.     

Electrical conductivity and molecular properties of organodithioheterobimetallics [PhHg]2[M(dithio)2] {M=Ni, Cu or Zn; dithio=isomaleonitriledithiolate (i-MNT) 1,1-dicarboethoxy-2,2-ethylenedithiolate (DED) or trithiocarbonate (CS3)}

Organoheterobimetallic compounds of the type, [PhHg]₂[M(dithio)₂] {M=Ni(II), Cu(II) or Zn(II); dithio=isomaleonitriledithiolate (i-MNT²⁻), 1,1-dicarboethoxy-2,2-ethylenedithiolate (DED²⁻) or trithiocarbonate (CS₃²⁻)} have been synthesized and investigated by molecular spectroscopies and conductivity techniques. Magnetic behaviour, together with electronic spectra, are compatible with square planar coordination geometry around nickel(II) in [PhHg]₂[Ni(dithio)₂]. Magnetic moments, 1.6 BM and 1.25 BM for [PhHg]₂[Cu(i-MNT)₂] and [PhHg]₂[Cu(DED)₂] showed involvement of some sort of Cu–Cu interaction. Their electronic and EPR spectra show distorted square planar geometry with tetragonal/rhombic symmetry around copper(II). Powder X-ray diffraction patterns of the complexes have been compared. All the complexes show σ_rt in 2.29×10⁻¹⁰−4.38×10⁻⁴ S cm⁻¹ range. [PhHg]₂[Ni(DED)₂] and [PhHg]₂[Cu(i-MNT)₂] show semiconducting behaviour as their conductivity increases with increase in temperature with band gaps 0.39 eV; 0.57 eV and 2.38 eV, respectively.     

Optical study of praseodymium dicarboxylate [Pr(H2O)]2[O2C(CH2)3CO2]3.4H2O

Praseodymium dicarboxylate, [Pr(H₂O)]₂[O₂C(CH₂)₃CO₂]₃.4H₂O]–glutarate, Pr[glut], is synthesized by hydrothermal techniques. The title compound crystallizes in the monoclinic space group C2/c (No. 15). The rare earth cation is coordinated by nine oxygen atoms, eight oxygen atoms from the carboxylate groups and one from the water molecule. The local symmetry of Pr site is low, C_s. The absorption spectra of Pr[glut] are recorded from the visible to the far IR domain at 300, 77 and 9 K. Under various Ar⁺ laser excitations no emission is detected from ³P₀ and ¹D₂ excited levels of Pr³⁺ ion. In the low temperature absorption spectra only one electronic line is recorded for ³H₄→³P₀ transition. It confirms a unique local environment for the rare earth ion in Pr[glut]. The utility of the ‘barycenter curves’ in the attribution of electronic lines is demonstrated. Energy level scheme of 36 Stark components is deduced from the absorption spectra. The parametric calculation was performed on the whole 4f² (Pr³⁺) configuration with the starting set of crystal field parameters obtained previously for the Eu³⁺ ion in the isostructural compound. Eight free ion and nine phenomenological crystal field parameters in C_2v symmetry reproduce quite well several electronic levels of Pr³⁺ ion experimentally observed in Pr[glut]. A good r.m.s. standard deviation of 14.8 cm⁻¹ is obtained.     

Kinetic study on Li2.8(V0.9Ge0.1)2(PO4)3 by EIS measurement

Kinetics for lithium ion transfers in the fast ionic conductor Li_2.8(V_0.9Ge_0.1)₂(PO₄)₃ prepared by solid-state reaction method has been studied by electrochemical impedance spectroscopy (EIS) at various temperatures and the results were correlated with observed cathodic behavior. The specific conductivities of Li_x(V_0.9Ge_0.1)₂(PO₄)₃ (x = 0.9–2.8) versus temperatures were analyzed from blocking-electrodes by Wagner's polarization method and the activation energy was calculated. It was observed that electronic conductivities of Li_x(V_0.9Ge_0.1)₂(PO₄)₃ increased with lithium contents in the materials. The compounds show a reversible capacity of 131 mAh g⁻¹ at low current density (13 mA g⁻¹). Modeling the EIS data with equivalent circuit approach enabled the determination of charge transfer and surface film resistances. The Li ion diffusion coefficient (D_Li⁺) versus voltage plot shows three valleys during the first charge cycle coinciding with the irreversible plateau of the voltage versus lithium content profiles reflecting the irreversible phase change in the compound. The obtained D_Li⁺ from EIS varies within 10⁻⁸ to 10⁻⁷ cm² s⁻¹, so Li_2.8(V_0.9Ge_0.1)₂(PO₄)₃ shows excellent chemical diffusion performance.     

Synthesis and properties of lithium ion conductors Li3−2x(Sc1−xZrx)2(PO4)3

Lithium ion conductors, Li_3−2x(Sc_1−xZr_x)₂(PO₄)₃ (0 x 0.3), were prepared by a solid-state reaction. TG–DTA analysis indicated no phase transition in the samples with x superior to 0.05. X-ray powder diffraction analysis of these samples clearly showed the stabilization of a superionic conduction phase at room temperature with an orthorhombic system Pbcn. The highest conductivity was observed for the sample with x=0.05, and ascribed to the stabilization of the superionic conduction phase and the introduction of vacancies on the Li⁺ sites by substituting Zr⁴⁺ for Sc³.     

Crystal structures and structural relationships of KFe2(SeO2OH)(SeO3)3 and SrCo2(SeO2OH)2(SeO3)2

The new phases KFe₂(SeO₂OH)(SeO₃)₃ and SrCo₂(SeO₂OH)₂(SeO₃)₂ have been synthesized under low-hydrothermal conditions and their structures were determined by single-crystal X-ray methods. Both compounds are monoclinic; KFe₂(SeO₂OH)(SeO₃)₃: space group P2, A = 9.983(4), B = 5.270(1), C = 10.614(4) Å, β = 97.42(2)°, V = 553.7 ų, Z = 2; SrCo₂(SeO₂OH)₂(SeO₃)₂: space group P2ln, A = 14.984(2), B = 5.286(1), C = 13.790(2) Å, β = 94.72(1)°, V = 1088.5 ų , Z = 4. The refinements converged to R-values of 2.9 and 3.6% respectively.

The atomic arrangement in KFe₂(SeO₂OH)(SeO₃)₃ and SrCo₂(SeO₂OH)₂(SeO₃)₂ is based on isolated MO₆ octahedra (M = Fe³⁺, Co²⁺), which are corner-linked via trigonal pyramidal selenite groups to a framework structure. Interstitials are occupied by potassium or strontium atoms in ten- or eight-coordination respectively, and by the lone-pair electrons of the Se⁴⁺ atoms. Both compounds are not isotypic but are closely related and may be interpreted as different distortions of an idealized structure type in space group P2/m, which was modelled for a theoretical compound SrFe₂(SeO₃)₄ by distance least squares refinement (program ).     

Structural, magnetic and magnetostrictive studies of Tb0.27Dy0.73(Fe1 − xAlx)2

Measurements of magnetic properties, X-ray diffraction and magnetostriction were made on Tb_0.27Dy_0.73(Fe_{1 − x}Al_x)₂ (x = 0.1, 0.2, …, 0.7) compounds. It was found that the system has the cubic MgCu₂ structure over almost the whole (Fe,Al) concentration range investigated, except for a narrow intermediate range (x = 0.4–0.6) where the hexagonal MgZn₂ structure appears. With increasing Al content x, the lattice constant a increases linearly with x. The first replacement of Fe results in a marked decrease in the Curie temperature, which is followed by a slight decrease in T_C with x. A linear decrease in magnetostriction of |λ_| − λ| at room temperature with x was also observed from 1530 × 10⁻⁶ for x=0 to 36×10⁻⁶ for x=0.3. The saturation magnetization σ_s exhibits a complex concentration dependence in the Tb_0.27Dy_0.73(Fe)_{1 − x}Al_x)₂ system: in the range x < 0.5, σ_s increases linearly with x and, for x = 0.5–0.6, σ_s decreases and then increases again. An enhancement of the magnetic ‘hardness’ in this system was also observed at low temperature.     

Luminescence based on energy transfer in xerogels doped with Ln2−xTbx(WO4)3

This paper presents preparation, optical absorption and photoluminescence properties of luminescent materials consisting of Ln_2−xTb_x(WO₄)₃ [where Ln = Gd(III) or La(III)] incorporated into silica xerogel. Photoluminescence behaviour of the salt in the rigid matrix was studied by the luminescence spectroscopy. The excitation spectra of the system Ln_2−xTb_x(WO₄)₃ show an intense broad band with a maximum placed at about 240 nm. This band is attributed to ligand–metal charge transfer (LMCT) inside the tungstate group. On the other hand, Tb³⁺ ion exhibits its characteristic emission in the material. Owing to energy transfer from the excited tungstate groups to the Tb³⁺ ions the emission intensity is improved. The energy transfer from WO₄²⁻ group to Tb(III) ion is particularly effective for such dopants as Gd_0.4Tb_1.6(WO₄)₃ or La_0.8Tb_1.2(WO₄)₃ incorporated into SiO₂ xerogel. Concentration of the emission quenchers such as water molecules and OH groups was reduced by thermal treatment. The high emission intensity and easy preparation of these systems make them potential candidates for application as luminescent materials.     

Low-frequency Raman spectra in κ-(BEDT-TTF)2Cu(NCS)2 and κ-(BEDT-TTF)2Cu[N(CN)2]Br

The ordering of the terminal ethylene groups of the BEDT-TTF molecule, i.e., the staggered or eclipsed conformation, in κ-(BEDT-TTF)₂Cu(NCS)₂ and κ-(BEDT-TTF)₂Cu[N(CN)₂]Br was studied between 18 and 295 K by Raman scattering. The low-frequency spectra of these compounds are similar to each other. Broad peaks at about 55 cm⁻¹ extremely broadened and their intensities became weak with decreasing temperature. The anomalous behaviour was interpreted in terms of critical dynamics of the pseudospin-phonon coupled system, where the spin states represent the conformations of the terminal ethylene groups. It was found that the ordered state is formed around the superconducting critical temperature.     

Spectroscopy, magnetism and non-radiative processes in heteronuclear Cu:Pr squarate; [Pr2Cu(C4O4)4(H2O)16]·2H2O

In the present work, the spectroscopic and magnetic properties of heteronuclear Cu:Pr squarate are reported. Single crystals of [Pr₂Cu(C₄O₄)₄(H₂O)₁₆]·2H₂O were obtained by reaction of squaric acid, praseodymium chloride and copper chloride in water solution according to the procedure described earlier. The crystals of title compound are isomorphic with [La₂Cu(C₄O₄)₄(H₂O)₁₆]·2H₂O crystal, where squarate anions participate as bridging ligands between metal ions.

The UV region of absorption spectra of the title compound is dominated by C–T band of Cu(II), f–d transition of Pr(III) and internal π–π*(A_1g→E_u) and π–π*(A_1g→E_g) ligand transitions. In visible and IR regions, t_2g–e_g of copper Cu(II) as well as ³H₄→³P_J, ¹D₂, ¹G₄, ³F_J, ³H₆ Pr(III) transitions at 293 and 4 K were recorded. At low temperature splitting given by Jahn–Teller effect can be observed. Significant anisotropy of d–d transitions intensities confirms well the Jahn–Teller effect, too. Unexpectedly high intensity of ³H₄→¹G₄ transition is probably due to the intensity borrowing from the Cu (II) d–d transition.

The ³P₀ and ¹D₂ emission of Pr(III) in the [Pr₂Cu(C₄O₄)₄(H₂O)₁₆]·2H₂O crystals is quenched even at 77 K. Whereas emission of appropriate polynuclear europium squarate was detected. The pathways of excited state quenching by e_g levels of Cu(II), multhiphonon relaxation and concentration quenching can be considered in the system under studies. Magnetic susceptibility measurements were carried out in 300–1.7 K temperature range and are discussed in relation to the structure.

Effect of the polymeric structure on spectroscopic behaviour is presented. Selectivity of polymeric europium squarate in vitro test for different tumor cells is shown.     

New organic superconductor, λ-(BETS)2GaCl4 and metal-insulator transition of BETS conductor with magnetic anions (BETS = bis(ethlenedithio)tetraselenafulvalene)

Crystal structutres and electronic properties of BETS compounds with tetrahedral anions, MX₄ (BETS = bis(ethylenedithio)tetraselenafulvalene; M = Ga, Fe, In; X = Cl, Br) were examined. The salts can be classified into two types (κ, λ). All the compounds with so-called κ-type molecular arrangements retained metallic behavior down to 4 K. λ-(BETS)₂GaCl₄ demonstrated a a superconducting transition around 8 K. Whereas λ-(BETS)₂FeCl₄ with the isomorphic λ-type structure exhibited a sharp metal-insulator transition at 8 K. Low-temperature X-ray studies showed that the structural difference between λ-GaCl₄ and λ-FeCl₄ salts is very small. The structure analysis of κ-(BETS)₂FeCl₄ at 18 K indicated that the FeCl₄ anion has approximately C_3v symmetry. The ESR measurements revealed the high-spin state of Fe³⁺ in λ-FeCl₄ salt and and low-spin state in κ-FeCl₄ salt. ESR intensities of κ- and λ-FeCl₄ salts suggested antiferromagnetic interaction between Fe³⁺ ions.     

Synthesis, crystal structure and properties of the new semiconductor (EVT)4·[Pt(CN)4]

A novel radical cation salt based on of the donor (4,5-ethylenedithio-4′,5′-vinylenedithio)tetrathiafulvalene (EVT) with the square planar anion Pt(CN)₄²⁻ has been synthesized: (EVT)₄·[Pt(CN)₄] (1). According to the X-ray analysis its crystal structure includes EVT cation layers alternating with anion layers along the a-axis of the unit cell. The radical cation layer is formed by EVT stacks with β-packing type, the donors in stacks are tetramerized. The EPR spectra of a plate-like crystal of (EVT)₄·[Pt(CN)₄] salt shows a very weak signal with typical parameters of TTF derivative. The room temperature conductivity of salt 1 is 8×10⁻² Ω⁻¹ cm⁻¹ and the temperature dependence of the conductivity exhibits semiconducting character.     

Phase transition of γ-(BEDT-TTF)3(HSO4)2

The structural properties and the metal-insulator (MI) transition of γ-ET₃(HSO₄)₂ (1) are discussed, in comparison with those of γET₃(ClO₄)₂ (2). Transition of 1 is related to a structural change, as in the case of 2. The substitution of hydrogen of the anion with deuterium lengthens the O O distance of intermolecular hydrogen bonds between the two anions, although an MI transition temperature is not changed appreciably. The hydrogen bonds between the two anions make the rotation of the anion molecules strongly hindered and shift their positions close to each other, which enables the puckering motion of the ethylene bridge of ET molecules easily.     

Fabrication and electrical and thermal properties of Ti2InC, Hf2InC and (Ti,Hf)2InC

In this paper we report on the characterization of predominantly single phase, fully dense Ti₂InC (Ti_1.96InC_1.15), Hf₂InC (Hf_1.94InC_1.26) and (Ti,Hf)₂InC ((Ti_0.47,Hf_0.56)₂InC_1.26) samples produced by reactive hot isostatic pressing of the elemental powders. The a and c lattice parameters in nm, were, respectively: 0.3134; 1.4077 for Ti₂InC; 0.322, 1.443 for (Ti,Hf)₂InC; and 0.331 and 1.472 for Hf₂InC. The heat capacities, thermal expansion coefficients, thermal and electrical conductivities were measured as a function of temperature. These ternaries are good electrical conductors with a resistivity that increases linearly with increasing temperatures. At 0.28 μΩ m, the room temperature resistivity of (Ti,Hf)₂InC is higher than the end members (0.2 μΩ m), indicating a solid solution scattering effect. In the 300 to 1273 K temperature range the thermal expansion coefficients are: 7.6×10⁻⁶ K⁻¹ for Hf₂InC, 9.5×10⁻⁶ K⁻¹ for Ti₂InC, and 8.6×10⁻⁶ K⁻¹ for (Ti,Hf)₂InC. They are all good conductors of heat (20 to 26 W/m K) with the electronic component of conductivity dominating at all temperatures. Extended exposure of Ti₂InC to vacuum (10⁻⁴ atm) at 800 °C, results in the selective sublimation of In, and the conversion of Ti₂InC to TiC_x.     

High resolution NMR and structural investigations of the 2-ammonium 2-methyl propanol dihydrogenodiphosphate [(CH3)2C(NH3)CH2OH]2H2P2O7

We report on high resolution ¹³C and ³¹P NMR and X-ray diffraction measurements of the organic dihydrogenodiphosphate (C₄H₁₂NO)₂H₂P₂O₇. The obtained ¹³C magic angle spinning (MAS) NMR spectrum at room temperature shows four resonances at 22, 23, 57 and 66 ppm which we attribute to the four magnetically inequivalent carbons of the organic cation, the two CH₃, the CH₂ and the quaternary carbon, respectively. The corresponding ³¹P MAS NMR spectrum presents two isotropic resonances at − 9.2 and − 6.9 ppm assigned to the two crystallographically inequivalent sites of the phosphorus atoms in the structure. The obtained NMR results are in quite good agreement with our X-ray data on the same sample. These results confirm the non-centrosymmetric structure of this material and its ability to exhibit non-linear optical properties.     

The electronic structure of organometallic complexes of the f elements XLI: Crystal field strength of η-cyclooctatetraenyl ligand estimated on the basis of the preliminary crystal field parameters of (COT)Nd[HB(3,5-Me2pz)3]

The absorption spectrum of (η⁸-COT)Nd[HB(3,5-Me₂pz)₃] (COT=cyclooctatetraenyl, pz=pyrazol-1-yl) has been measured at room temperature, at approximately 90 K and in parts at ca. 30 K. The bands were assigned by applying the selection rules for C_8v symmetry and by performing crystal field (CF) calculations assuming the CF parameters of the Nd complex were the same as for the previously analyzed (COT)Pr[HB(3,5-Me₂pz)₃]. The parameters of an empirical Hamiltonian were fitted to the energies of 27 levels to give an r.m.s. deviation of 25.5 cm⁻¹. Neglecting the influence of [HB(3,5-Me₂pz)₃] ligand, the CF strength of the [COT]⁻⁻ ligand could be estimated from the CF parameters obtained.     

Raman active phonons of RFe3(BO3)4, R=La or Nd, single crystals

Oriented single crystals of RFe₃(BO₃)₄, with R=La or Nd, have been studied by Raman spectroscopy. Spectra with the relevant polarization configurations have been recorded in order to obtain the symmetry of the observed phonons. The factor group analysis and the correlation with the free (BO₃)³⁻ ion are done in order to identify most of the phonons associated with the two different types of (BO₃)³⁻ ion present in the crystal. The number and symmetries of the optical Raman active modes are 7A₁+19E, among which 4A₁+8E can be assigned as mostly due to (BO₃)³⁻ vibrations. 7A₁+18E modes were observed.

The highest energy peaks have been assigned to the regular planar (BO₃)³⁻ and to the three irregular (BO₃)³⁻ groups. The two lowest energy peaks of A₁ symmetry (around 180 and 300 cm⁻¹) are very probably related to the BO₃ rotatory mode and to Fe displacements. R ions do not participate in A₁ symmetry modes. The E mode around 90 cm⁻¹ (the lowest frequency mode) is probably due to the R ions which have the longest bonds and are the heaviest ions.     

-NMRC-NMR study on κ-(BEDT-TTF)2X

The electronic state of the κ phase family of BEDT-TTF compounds, κ-(BEDT-TTF)₂X [X = Cu(NCS)₂, Cu[N(CN)₂]Br and Cu[N(CN)₂]Cl], has been investigated by -NMR¹³C-NMR as well as H-NMR.¹-NMR. The ¹³C isotope was substituted selectively into the central double bonded carbon sites of BEDT-TTF. The ¹³C nuclear spin-lattice relaxation rate and line spectra have been measured for the Cu(NCS)₂ and Cu[N(CN)₂]Br salts. The Knight shift evaluated from the the width of the spectra of the powdered samples is temperature-insensitive and scaled to the uniform susceptibility. However, the relaxation rate, T₁⁻¹, does not obey the Korringa law but exhibits anomalous temperature dependence with a peak formation around 50 K. The absolute value of T₁⁻¹ is in excess of the Korringa relation. These behaviors are considered to come from strong aniferromagnetic spin fluctuation with finite wave vector, which is suppressed below 50 K. On the other hand, the H¹ NMR and magnetization measurements gave an unambiguous evidence for antiferromagnetic transition with spin canting at 25 K in κ-(BEDT-TTF)₂Cu[N(CN)₂]Cl. The κ phase family, situated in the vicinity of metal-insulator and magnetic transitions, is characterized by strong electron correlations.     

Vaporization behavior and thermodynamic stability of V2P(s)

The vaporization behavior and thermodynamic stability of V₂P(s) were investigated by mass loss effusion and effusion mass spectrometry, the latter by an ion current ratio method. Enthalpies of formation with white phosphorus as the reference state and enthalpies of atomization were calculated. Results from the two types of experiments are in good agreement. Mean values of V₂P(s): Δ_fH°_298.15 = −209.0±5 kJ mol⁻¹, Δ_atH°_298.15 = 1556.4 kJ mol⁻¹. Recalculated values for V₃P(s): Δ_fH°_298.15 = −233.13±5 kJ mol⁻¹, Δ_atH°_298.15 = 2096.0 kJ mol⁻¹.