Synthesis,second-harmonic generation (SHG), and photoluminescence (PL) properties of noncentrosymmetric bismuth selenite solid solutions,Bi2-xLnxSeO5 (Ln = La and Eu; x = 0–0.3)

A series of La³⁺ or Eu³⁺-doped noncentrosymmetric (NCS) bismuth selenite solid solutions, Bi_2-xLn_xSeO₅ (x = 0.1, 0.2, and 0.3), have been successfully synthesized via standard solid-state reactions under vacuum with Bi₂O₃, La₂O₃ (or Eu₂O₃), and SeO₂ as starting materials. Crystal structures and phase purities of the resultant materials were thoroughly characterized by powder X-ray diffraction using the Rietveld method. The results clearly show that the reported materials crystallize in the orthorhombic space group, Abm2 (No. 39), and exhibit pseudo-three-dimensional frameworks consisting of BiO₃, BiO₅, and SeO₃ polyhedra that share edges and corners. Detailed diffraction studies indicate that the cell volume of Bi_2-xLn_xSeO₅ decreases with an increasing amount of Ln³⁺ on the Bi³⁺ sites. However, no ordering between Ln³⁺ and Bi³⁺ was observed in the Bi_2-xLn_xSeO₅ solid solutions. Powder second-harmonic generation (SHG) measurements, using 1064 nm radiation, reveal that SHG efficiencies of Bi_2-xLn_xSeO₅ solid solutions continuously decrease as more Ln³⁺ cations are added to the sites of polarizable Bi³⁺ cations. Photoluminescence (PL) measurements on Bi_2-xEu_xSeO₅ exhibit three specific emission peaks at 592, 613, and 702 nm (⁵D₀ → ⁷F_{1, 2, 4}) owing to the 4f-4f intrashell transitions of Eu³⁺ ions.     

Les phases SrLnMnO4 (Ln = La,Nd, Sm,Gd), BaLnMnO4 (Ln = La,Nd) et M1+xLa1−xMnO4 (M = Sr,Ba)

The phases SrLnMnO₄ (Ln = La, Nd, Sm, Gd), BaLnMnO₄ (Ln = La, Nd) and the solid solutions M_1+xLa_1?xMnO₄ (M = Sr: 0 ? x ? 1; M = Ba: 0 ? x ? 0.50) have a K₂NiF₄-type structure. The $\text{c}\text{a}$ ratio of the unit cell is related to the electronic configuration of the Mn³⁺ ions.     

Isomorphous substitution of samarium and gadolinium for calcium in hydroxyapatite structure

Isomorphous substitution of samarium and gadolinium for calcium in synthetic hydroxyapatite by the scheme Ca²⁺ + OH⁻ → Ln³⁺ + O²⁻ was studied by X-ray powder diffraction and IR spectroscopy. The homogeneity region of Ca_{10 − x} Ln _x (PO₄)₆(OH)_{2 − x} O _x phases of variable compositions synthesized at 1100°C was found to exist up to x of 1.8 for Sm and 1.4 for Gd. In the heterogeneous region of solid solutions, phases with Ln₃PO₇ and LnPO₄ structures were formed. The structures of some solid solutions were refined by the Rietveld method, which allowed us to establish that the substitution of Ln³⁺ ions for Ca(2) positions is preferred. Changes in the intensities of the absorption bands of stretching and libration vibrations of OH groups are indicative of a partial dehydration of oxyhydroxyapatite. The substitution was shown to decrease Ca(2)-O(OH) and P-O distances and increase Ca(2)-O(1,2,3) distances.     

Stuffed rare earth pyrochlore solid solutions

Synthesis and crystal structures are described for the compounds Ln₂(Ti_2−xLn_x)O_7−x/2, where Ln=Tb, Dy, Ho, Er, Tm, Yb, Lu, and x ranges from 0 to 0.67. Rietveld refinements of X-ray powder diffraction data indicate that in the Tb and Dy titanate pyrochlores, the extra Ln³⁺ cations mix mainly on the Ti⁴⁺ site with little disorder on the original Ln³⁺ site. For the smaller rare earths (Ho-Lu), stuffing additional lanthanide ions results in a pyrochlore to defect fluorite transition, where the Ln³⁺ and Ti⁴⁺ ions become completely randomized at the maximum (x=0.67). Initial magnetic characterization for the fully stuffed x=0.67 samples for Ln=Tb-Yb shows no long range ordering down to 2 K, and only partial saturation of the full expected magnetic moment under applied fields up to 5 T. In all of these Ln-Ti-O pyrochlores, the addition of magnetic Ln³⁺ in place of non-magnetic Ti⁴⁺ adds edge sharing tetrahedral spin interactions to a normally corner sharing tetrahedral network of spins. The increase in spin connectivity in this family of solid solutions represents a new avenue for investigating geometrical magnetic frustration in the rare earth titanate pyrochlores.     

Single-Crystal-to-Single-Crystal Installation of Ln4(OH)4 Cubanes in an Anionic Metallosupramolecular Framework

Postsynthetic installation of lanthanide cubanes into a metallosupramolecular framework via a single-crystal-to-single-crystal (SCSC) transformation is presented. Soaking single crystals of K₆[Rh₄Zn₄O(l -cys)₁₂] (K₆[ 1 ]; l -H₂cys=l -cysteine) in a water/ethanol solution containing Ln(OAc)₃ (Ln³⁺=lanthanide ion) results in the exchange of K⁺ by Ln³⁺ with retention of the single crystallinity, producing Ln₂[ 1 ] ( 2_Ln ) and Ln_0.33[Ln₄(OH)₄(OAc)₃(H₂O)₇][ 1 ] ( 3_Ln ) for early and late lanthanides, respectively. While the Ln³⁺ ions in 2_Ln exist as disordered aqua species, those in 3_Ln form ordered hydroxide-bridged cubane clusters that connect [ 1 ]⁶⁻ anions in a 3D metal-organic framework through coordination bonds with carboxylate groups. This study shows the utility of an anionic metallosupramolecular framework with carboxylate groups for the creation of a series of metal cubanes that have great potential for various applications, such as magnetic materials and heterogeneous catalysts.     

High-temperature calorimetry of (La1−xLnx)PO4 solid solutions

The enthalpy increment of the monazite-type solid solutions of LaPO₄ with NdPO₄, EuPO₄ and GdPO₄ has been measured by drop calorimetry at T = 1000 K. The results show deviations (excess enthalpy) from ideal behaviour that have been interpreted in terms of lattice strains resulting from the ion size effects of substitution of La³⁺ by Ln³⁺. For (La_0.5Gd)_0.5PO₄ also the temperature dependence has been determined for T = (515 to 1565) K, indicating that the excess enthalpy decreases with increasing temperature.     

Synthesis,Structures, and Magnetic Properties of Zigzag Tetranuclear Lanthanide Complexes

Five isostructural tetranuclear lanthanide complexes with the general formula [Ln₄(teaH₂)₂(teaH)₂(NO₃)₆] · 2CH₃OH [Ln³⁺ = Dy³⁺ ( 1 ), Tb³⁺ ( 2 ), Ho³⁺ ( 3 ), Er³⁺ ( 4 ), and Gd³⁺ ( 5 )] were successfully synthesized by the reaction of various lanthanide nitrate and triethanolamine (teaH₃) ligand. Single crystal X-ray analyses reveal the eight-coordinate Ln³⁺ centers adopt a slightly distorted triangular dodecahedron geometry and nine-coordinate Ln³⁺ ions own an approximately capped square antiprism environment in similar zigzag Ln4 core. Magnetic studies demonstrate the presence of anitferromagnetic interactions between Ln³⁺ centers without obvious SMM behavior.     

Intermolecular dynamics and paramagnetic properties of ethylenediaminetetraacetate complexes with the yttrium subgroup rare earth elements using nuclear magnetic resonance

¹H nuclear magnetic resonance (NMR) measurements are reported for the D₂O solutions of [Ln³⁺(EDTA^4?)]^? complexes, where EDTA^4? is ethylenediaminetetraacetate anion, Ln³⁺ = Tb³⁺ (I), Ho³⁺ (II), Tm³⁺ (III), Yb³⁺ (IV) and Lu³⁺ (V). Temperature dependencies of the ¹H NMR spectra of paramagnetic I–IV have been analyzed using the dynamic NMR methods. It is found that the activation free energies (ΔG^?₂₉₈ ) of the intermolecular EDTA ions exchange at [Ln³⁺(EDTA^4?)]^? complexes are 60±3 (I), 66±3 (II), 69±3 (III) and 74±3 (IV) kJ/mol (at pD = 7). A monotonic increase of the free energy of chemical exchange processes along the series of lanthanide [Ln³⁺ (EDTA^4?)]^? complexes is probably related to the lanthanide contraction. The obtained results indicate that coordination compounds I–IV may be considered as thermometric NMR sensors and lanthanide paramagnetic probes for in situ temperature control in solution. Copyright © 2012 John Wiley & Sons, Ltd.     

Magnetic Properties of LnMnO3 (Ln=Ho, Er, Tm, Yb, and Lu)

Magnetic data are presented for LnMnO₃ (Ln=Ho, Er, Tm, Yb, and Lu) having the hexagonal crystal structure of P6₃cm. DC magnetization measurements show that magnetic order is not clearly observed for Ln=Ho-Yb, while an antiferromagnetic transition of the Mn³⁺ moments is found at ∼90 K for LuMnO₃, where the Lu³⁺ ion has no 4f localized moment. This is ascribed to both the paramagnetism of Ln³⁺ and the suppression of magnetization in the Mn³⁺ sublattices arising from strong antiferromagnetic interactions between Mn³⁺. Deviation from the Curie-Weiss law at low temperatures indicates the onset of antiferromagnetism. Some magnetization data of Ca-substituted compounds, Ln_0.5Ca_0.5MnO₃, which have the different crystal structure of orthorhombic Pnma, are also discussed briefly.     

Excess properties of the (Ln2−2xCaxThx)(PO4)2 (Ln = La, Ce) solid solutions

X-ray powder diffraction at room temperature and drop calorimetry at T = 1005 K were performed on LnPO₄–CaTh(PO₄)₂ (Ln = La, Ce) solid solutions. The results show excess molar volume and excess enthalpy indicating deviations from ideal behaviour that have been interpreted in terms of lattice strains resulting from the ion size effects of substitution of the Ln³⁺ with (Ca²⁺ + Th⁴⁺).     

Critical covalence and superconductivity in Ln2−xCexCuO4

The variations of superconductive properties with x of the n-type Ln_2−xCe_xCuO₄ (Ln = La_0.5Nd_0.5, Nd, or Gd) systems have been investigated. As the size of Ln³⁺ decreases, (i) the solubility limit x of Ce decreases, (ii) the value of x at which a transition from antiferromagnetic semiconductor to superconductor occurs increases, and (iii) the width Δx of the superconductive region decreases. The decreasing solubility of Ce with decreasing size of Ln³⁺ is due to decreasing tensile strain in the CuO₂ sheets. The progressive shift of the semiconductor to superconductor transition to higher x values with decreasing size of Ln³⁺ is explained on the basis of increasing electrostatic Madelung energy E_M caused by decreasing Cu---O bond length. A larger E_M means a larger charge transfer gap Δ and a smaller covalent-mixing parameter λ and bandwidth W; so a decreasing size of Ln³⁺ necessitates a higher level of Ce-doping in order to achieve a critical covalence essential for superconductivity to occur.     

Single‐Crystal‐to‐Single‐Crystal Installation of Ln4(OH)4 Cubanes in an Anionic Metallosupramolecular Framework

Postsynthetic installation of lanthanide cubanes into a metallosupramolecular framework via a single‐crystal‐to‐single‐crystal (SCSC) transformation is presented. Soaking single crystals of K₆[Rh₄Zn₄O(l ‐cys)₁₂] (K₆[ 1 ]; l ‐H₂cys=l ‐cysteine) in a water/ethanol solution containing Ln(OAc)₃ (Ln³⁺=lanthanide ion) results in the exchange of K⁺ by Ln³⁺ with retention of the single crystallinity, producing Ln₂[ 1 ] ( 2_Ln ) and Ln_0.33[Ln₄(OH)₄(OAc)₃(H₂O)₇][ 1 ] ( 3_Ln ) for early and late lanthanides, respectively. While the Ln³⁺ ions in 2_Ln exist as disordered aqua species, those in 3_Ln form ordered hydroxide‐bridged cubane clusters that connect [ 1 ]^6? anions in a 3D metal‐organic framework through coordination bonds with carboxylate groups. This study shows the utility of an anionic metallosupramolecular framework with carboxylate groups for the creation of a series of metal cubanes that have great potential for various applications, such as magnetic materials and heterogeneous catalysts.     

Synthesis of New LnxBi2–xSe3 (Ln: Sm3+, Eu3+, Gd3+, Tb3+) Nanomaterials and Investigation of Their Optical Properties

New Ln_xBi_2–xSe₃ (Ln: Sm³⁺, Eu³⁺, Gd³⁺, Tb³⁺) based nanomaterials were synthesized by a co‐reduction method. Powder XRD patterns indicate that the Ln_xBi_2–xSe₃ crystals (Ln = Sm³⁺, Eu³⁺, x = 0.00–0.44 and Ln = Gd³⁺, Tb³⁺, x = 0.00–0.50) are isostructural with Bi₂Se₃. The cell parameter c decreases for Ln = Eu³⁺, Gd³⁺, Tb³⁺ upon increasing the dopant content (x), while a slightly increases. Changes in lattice parameters could be related to the radii of cations. SEM images show that doping of the lanthanide ions in the lattice of Bi₂Se₃ generally results in nanoflowers. For the terbium compound two kinds of morphologies (nanoflowers and nanobelts) were observed. UV/Vis absorption and emission spectroscopy reveals mainly electronic transitions of the Ln³⁺ ions. Emission spectra show intense transitions from the excited to the ground state of Ln³⁺ and energy transfer from the Bi₂Se₃ lattice. Emission spectra of europium‐doped materials, in addition to the characteristic red emission peaks of Eu³⁺, show an intense blue emission band centered at 432 nm, originating from the 4f⁶5d¹ to 4f⁷ configuration in Eu²⁺. EPR measurements confirm the existence of Eu²⁺ in the materials. Interestingly, for all samples starting at low Ln³⁺ concentration, the emission intensity rises to a maximum at a Ln³⁺ concentration of x = 0.2 and falls again steadily to a minimum at x = 0.45.     

Facile sonochemical synthesis and photoluminescent properties of lanthanide orthophosphate nanoparticles

Uniform lanthanide orthophosphate LnPO₄ (Ln=La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho) nanoparticles have been systematically synthesized via a facile, fast, efficient ultrasonic irradiation of inorganic salt aqueous solution under ambient conditions without any surfactant or template. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), selected area electron diffraction (SAED), photoluminescence (PL) spectra as well as kinetic decays were employed to characterize the samples. The SEM and the TEM images show that the hexagonal structured lanthanide orthophosphate LnPO₄ (Ln=La, Ce, Pr, Nd, Sm, Eu, Gd) products have nanorod bundles morphology, while the tetragonal LnPO₄ (Ln=Tb, Dy, Ho) samples prepared under the same experimental conditions are composed of nanoparticles. HRTEM micrographs and SAED results prove that these nanostructures are polycrystalline in nature. The possible formation mechanism for LnPO₄ (Ln=La-Gd) nanorod bundles is proposed. Eu³⁺-doped LaPO₄ and Tb³⁺-doped CePO₄ samples were also prepared by using the same synthetic process, which exhibit an orange-red (Eu³⁺:⁵D₀-⁷F_{1, 2, 3, 4}) and green (Tb³⁺, ⁵D₄-⁷F_{3, 4, 5, 6}) emission, respectively.     

Crystal chemical aspect of synthesis of laser crystals with garnet structure in Ln2O3−Sc2O3−M2O3 systems (Ln=Y,Gd; M=Ga,Al)

Regions of existence were determined for various types of poly- and monocrystalline solid solutions (Ln₃[Sc_yM_2−y]M₃O₁₂; {Ln_3−xSc_x}[Sc_yM_2−y]M₃O₁₂; Ln₃[Ln_zSc_yM_2−y−z] M₃O₁₂; Ln=Y, Gd; M=Ga, Al) by analyzing the diagrams r^VIII−r^VI (r^VI are weighted mean dodecahedral and octahedral radii, respectively). We found the position of congruently melting compositions in r^VIII−r^VI coordinates and optimal compositions for obtaining Nd³⁺- and Cr³⁺-doped crystals. The structure of the congruently melting composition was found to be formed of “equilibrium” polyhedra, which need not be stabilized. It is shown that a congruently melting composition, which is absent in the original matrix, may be achieved by isomorphous substitutions at certain positions of the structure. The most probable mechanisms of formation of poly- and monocrystalline solid solutions with garnet structure are suggested using the calculated binodal curves of decomposition. M. V. Lomonosov Moscow Academy of Fine Chemical Technology. Translated fromZhurnal Strukturnoi Khimii, Vol. 35, No. 5, pp. 23–33, September–October, 1994. Translated by O. Kharlamova     

Luminescence of NaGdFPO4:Ln after VUV excitation: A comparison with GdPO4:Ln (Ln=Ce, Tb)

The phosphors NaGdFPO₄:Ln³⁺ and GdPO₄:Ln³⁺ (for Ln³⁺=Ce³⁺ and Tb³⁺) were prepared by solid-state reaction technique, the VUV-vis spectroscopic properties of the phosphors were investigated, and we vividly compare the luminescence of Ce³⁺ and Tb³⁺ in the hosts. For phosphors GdPO₄:Ln³⁺, the band near 155 nm in VUV excitation spectrum is assumed to be the host-related absorption, and for NaGdFPO₄:Ln³⁺ the absorption is moved to longer wavelength, near 170 nm, showing the P-O bond covalency increased after fluoridation. The f-d transitions of Ce³⁺ and Tb³⁺ in the host lattices are assigned and corroborated, and it was found that the 5d states are with lower energy in NaGdFPO₄:Ln³⁺ than those in GdPO₄:Ln³⁺. For fluoridation of GdPO₄:Ln³⁺ to NaGdFPO₄:Ln³⁺, the energy change of Ln³⁺ (Ln=Ce, Tb) 5d states is consistent with that of host-related absorption.     

Sur une série de solutions solides de formule Ca2−xLnxMnO4 (Ln = Pr,Nd, Sm,Eu, Gd)

A new series of solid solutions Ca_2−xLn_xMnO₄ (Ln = Pr, Nd, Sm, Eu et Gd) in which manganese is found in both oxidation state of +III and +IV, have a structure derived from that of K₂NiF₄. The cationic distribution in sites of nine-fold coordination is random.     

Ethylation of methylarsenic(III) compounds by sodium tetraethylborate

The compounds MeAsBr₂ and Me₂AsBr at concentrations of (1–5) × 10^?3 M in acetone solution are ethylated in high yield by NaBEt₄ to MeEt₂As and Me₂EtAs, as shown by ¹H NMR spectroscopy. The extents of ethylation of MeAs²⁺ and Me₂As⁺ (expressed as ions, by convention) in aqueous acid solutions [at concentrations of (5–20) × 10^?6 M ] were investigated using cold trap/AA and GC AA procedures. The species Me₂As⁺ was ethylated (to give Me₂EtAs) in good yield (88%); in contrast, MeAs²⁺ produced the volatile trialkylarsine, MeEt₂As, in poor yield (30%). No volatile trialkylarsine could be obtained on treating inorganic arsenic(III) (As³⁺) solutions with NaBEt₄.     

Solvothermal syntheses, and characterization of [Ln(en)4(SbSe4)] (Ln=Ce, Pr) and [Ln(en)4]SbSe4·0.5en (Ln=Eu, Gd, Er, Tm, Yb): The effect of lanthanide contraction on the crystal structures of lanthanide selenidoantimonates(V)

Two types of lanthanide selenidoantimonates [Ln(en)₄(SbSe₄)] (Ln=Ce(1a), Pr(1b)) and [Ln(en)₄]SbSe₄·0.5en (Ln=Eu(2a), Gd(2b), Er(2c), Tm(2d), Yb(2e); en=ethylenediamine) were solvothermally synthesized by reactions of LnCl₃, Sb and Se with the stoichiometric ratio in en solvent at 140 °C. The four-en coordinated lanthanide complex cation [Ln(en)₄]³⁺ formed in situ balances the charge of SbSe₄³⁻ anion. In compounds 1a and 1b, the SbSe₄³⁻ anion act as a monodentate ligand to coordinate complex [Ln(en)₄]³⁺ and the neutral compound [Ln(en)₄(SbSe₄)] is formed. The Ln³⁺ ion has a nine-coordinated environment involving eight N atoms and one Se atom forming a distorted monocapped square antiprism. In 2a-2e the lanthanide(III) ion exists as isolated complex [Ln(en)₄]³⁺, in which the Ln³⁺ ion is in a bicapped trigonal prism geometry. A systematic investigation of the crystal structures reveals that two types of structural features of these lanthanide selenidoantimonates are related with lanthanides contraction across the lanthanide series. TG curves show that compounds 1a-1b and 2a-2e remove their organic components in one and two steps, respectively.     

Syntheses,characterization and thermal properties of the lanthanide complexes with 2-mercaptonicotinic acid and 1,10-phenanthroline

Fourteen new complexes with the general formula of Ln(Hmna)₃(phen) (H₂mna = 2-mercaptonicotinic acid and phen = 1,10-phenanthroline) were synthesized and characterized by elemental analyses, IR spectra and thermogravimetric analyses. In addition, molar specific heat capacities were determined by a microcalorimeter at 298.15 K. The IR spectra of the complexes showed that the Ln³⁺ coordinated with the oxygen atoms of H₂mna and the nitrogen atoms of phen. The complexes decomposed directly to oxides Ln₂O₃, CeO₂, Pr₆O₁₁, and Tb₄O₇ in one step. The values of molar specific heat capacities for fourteen solid complexes were plotted against the atomic numbers of lanthanide, which presented as “tripartite effect”. It suggested a certain amount of covalent character existed in the bond of Ln³⁺ and ligands, according with nephelauxetic effect of 4f electrons of rare earth ions. The article is published in the original.