Studies on organolanthanide complexes : LXIII. Synthesis, spectroscopic and X-ray crystallographic characterization of new early organolanthanide, organoyttrium hydride and organoholmium hydroxide complexes

Organolanthanide chloride complexes [(CH₃OCH₂CH₂C₅H₄)₂Ln(μ-Cl)]₂ (Ln = La, Pr, Ho and Y) react with excess NaH in THF at 45°C to give the dimeric hydride complexes [(CH₃OCH₂CH₂C₅H₄)₂Ln(μ-H)]₂, which have been characterized by IR, ¹H NMR, MS and XPS spectroscopy, elemental analyses and X-ray crystallography. [(CH₃OCH₂CH₂C₅H₄)₂Y(μ-H)]₂ crystallizes from THF/n-hexane at −30°C, in the triclinic space group P1 with a = 8.795(2) Å, b = 11.040(1) Å, c = 16.602(2) Å, = 93.73(1)°, β = 91.82(1)°, γ = 94.21(1)°, D_c = 1.393 gcm⁻³ for Z = 2 dimers. However, crystals of [(CH₃OCH₂CH₂C₅H₄)₂Ho(μ-OH)]₂ were obtained by recrystallization of holmium hydride in THF/n-hexane at −30°C, in the orthorhombic space group Pbca with a = 11.217(2) Å, b = 15.865(7) Å, c = 17.608(4) Å, D_c = 1.816 gcm⁻³ for Z = 4 dimers. In the complexes of yttrium and holmium, each Ln atom of the dimers is coordinated by two substituted cyclopentadienyl ligands, one oxygen atom and two hydrogen atoms (for the Y atom) or two hydroxyl groups (for the Ho atom) to form a distorted trigonal bipyramid if the C(η⁵)-bonded cyclopentadienyl is regarded as occupying a single polyhedral vertex.     

[Ho5(H2O)16(OH)2As6W64O220]25−, ein großes neuartiges Polyoxoanion aus trivakanten Keggin‐Fragmenten

[Ho₅(H₂O)₁₆(OH)₂As₆W₆₄O₂₂₀]^25?, a Large Novel Polyoxoanion from Trivacant Keggin Fragments The novel polyoxotungstate Na₇K₁₈[Ho₅(H₂O)₁₆(OH)₂As₆W₆₄O₂₂₀] · 56 H₂O ( 1 ) was synthesized in aqueous solution and characterized by X‐ray structure analysis, elemental analysis and IR spectroscopy. The anion in 1 represents one of the largest polyoxoanions known yet and exhibits an unusual arrangement of six Keggin units. It consists of six trivacant lacunary α‐B‐(AsW₉O₃₃)^9? Keggin fragments which are connected by a bridging [Ho₅W₁₀(H₂O)₁₆(OH)₂O₂₂]²⁹⁺ unit. The five Ho^III atoms are coordinated by eight oxygen atoms, forming a square‐antiprism.     

Room Temperature Ferromagnetism in Ga1-xHoxN (x=0.0 and 0.05) Diluted Magnetic Semiconductor Thin Films

Holmium doped GaN diluted magnetic semiconductor thin films have been prepared by thermal evaporation technique and subsequent ammonia annealing. X-ray diffraction mea-surements reveal all peaks belong to the purely hexagonal wurtzite structure. Surface mor-phology and composition analysis were carried out by scanning electron microscopy and energy dispersive spectroscopy respectively. The room temperature ferromagnetic proper-ties of Ga_1-xHo_xN(x=0.0, 0.05) films were analyzed using vibrating sample magnetometer at room temperature. Magnetic measurements showed that the undoped films (i.e. GaN) exhibited diamagnetic behavior, while the Ho-doped (Ga_0.95Ho_0.05N) film exhibited a ferro-magnetic behavior.     

Effects of multi-dopants (Zn and Ho) in stabilizing spinel structure for cathode materials in lithium rechargeable batteries—Novel chelated sol–gel synthesis

Multi-doped spinels, namely LiMn₂O₄ and LiZn_xHo_yMn_2−x−yO₄ (x = 0.10–0.18; y = 0.02–0.10), for use as cathode materials for lithium-ion rechargeable batteries were synthesized via sol–gel method, using lauric acid as the chelating agent, to obtain micron-sized particles. The physical properties of the synthesized samples were investigated using differential thermal analysis, Fourier-transform infrared spectroscopy, X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy, energy-dispersive X-ray analysis, and electrochemical methods. XRD showed that LiMn₂O₄ and LiZn_xHo_yMn_2−x−yO₄ have high degrees of crystallinity and good phase purities. The SEM images of LiMn₂O₄ showed an ice-cube morphology with particles of size 1 μm. Charge–discharge studies showed that undoped LiMn₂O₄ delivered the discharge capacity of 124 mA h/g with coulombic efficiency of 95% during the first cycle, whereas doped spinels delivered discharge capacities of 125, 120, and 127 mA h/g in the first cycle with coulombic efficiencies of 96%, 91%, and 91%, respectively.     

The Fourier Transform Emission Spectrum of BΠ1-XΣ Band-System of InCl

The emission spectrum of the B³Π₁-X¹Σ⁺ band-system of the InCl molecule has been recorded on a Fourier transform spectrometer at an apodized resolution of 0.025 cm⁻¹. The rotational structure of 1-0, 2-1, 0-0, 0-1, 1-2, 0-2, and 1-3 bands belonging to the B³Π₁-X¹Σ⁺ transition of In³⁵Cl has been analyzed and accurate equilibrium rotational constants of the B³Π₁ state, have been obtained. Precise Λ-doubling constants of the B³Π₁ state (v=0, 1, and 2) are also reported for the first time.     

Synthesis and crystal structure of binuclear molecule Ho<Subscript>2</Subscript>(2-FC<Subscript>6</Subscript>H<Subscript>4</Subscript>COO)<Subscript>6</Subscript>⋅4H<Subscript>2</Subscript>O

The complex Ho₂(2-FC₆H₄COO)₆?4H₂O has been synthesized and structurally characterized by single crystal X-ray diffraction methods. The complex crystallizes in the triclinic system with space group P \(\bar 1\), lattice parameters a = 9.293(8) Å, b = 9.845(8) Å, c = 12.703(11) Å, α = 85.470(14)^°, β = 87.537(12)^°, γ = 62.485(11)^°, V = 1027.5(15) ų, Z = 1, D_calc = 1.998 Mg/m³. The Ho³⁺ ion is in distorted monocapped square-antiprism coordination environment and is coordinated by nine oxygen atoms, seven from five 2-FC₆H₄COO^2? groups, two from two water molecules. Two Ho³⁺ ions are linked together by four bridging carboxylate groups to form a binuclear molecule with inversion center.     

The hydrogen‐bond effect on the high pressure behavior of hydrazinium monochloride

The first high pressure study of solid hydrazinium monochloride has been performed by in situ Raman spectroscopy and synchrotron X‐ray diffraction (XRD) experiments in diamond anvil cell (DAC) up to 39.5 and 24.6 GPa, respectively. The structure of phase I at room temperature is confirmed to be space group C2/c by the Raman spectral analysis and Rietveld refinement of the XRD pattern. A structural transition from phase I to II is observed at 7.3 GPa. Pressure‐induced position variation of hydrogen atoms in NH₃⁺ unit during the phase transition is attributed to the formation of N―H…Cl hydrogen‐bonds, which play a vital role in the stability and subsequent structural changes of this high energetic material under pressure. This inference is proved from the abnormal pressure shifts and obvious Fermi resonance in NH stretching mode of N₂H₅⁺ ion in the Raman experiment. Finally, a further transition from phase II to III accompanied with a slight internal distortion in the N₂H₅⁺ ions occurs above 19.8 GPa, and phase III persists up to 39.5 GPa. Copyright © 2015 John Wiley & Sons, Ltd.     

$^{1}_{\infty}\rm [Ho_{2}Cl_{6}\{1,3-Ph(CN)_{2}\}_{3}]$ – Eine zu Doppelsträngen kondensierte Variante der PaCl5‐Struktur in einem Selten‐Erd‐Benzodinitril‐Koordinationspolymer

– A Variant of the PaCl₅ Structure Condensed to Double Strands in a Rare Earth Benzodinitrile Coordination Polymer Single crystalline transparent pink (1,3‐Ph(CN)₂ = 1,3‐benzodinitrile, C₆H₄(CN)₂) was obtained by the reaction of anhydrous holmium trichloride with a melt of 1,3‐benzodinitrile at 175 °C. The trichloride structure is broken up by the dinitrile ligands and re‐arranged to double strands of edge connected pentagonal bipyramids of chlorine and nitrogen atoms. The structure can be deduced from the PaCl₅ structure type by condensation of two PaCl₅ strands and exchange of two chlorine atoms with nitrile groups. The double strands exhibit ligand free cavities of 600–800 pm diameter.