The influence of Yb3+ concentration on Yb:YAl3(BO3)4

The Yb:YAl₃(BO₃) ₄ crystals with different Yb³⁺ doping concentration have been grown by the flux method. The lattice parameters and decomposition of the Yb:YAl₃(BO₃)₄ crystal with different Yb³⁺ doping concentration were measured by X‐ray and DTA method. The transmission and fluorescence spectra of Yb³⁺:YAl₃(BO₃)₄ crystal have been measured. The growth defects of Yb_xY_1‐xAl₃(BO₃)₄ crystals were also detected by using the chemical etching method. The results show that the ytterbium concentration influences these properties of Yb:YAl₃(BO₃)₄. As the Yb³⁺ concentration increased, the crystal lattice parameter was decreased. At high doping level, the absorption peak concerned at about 980 nm shift to short wavelength. It is also found that the perfection of Yb:YAl₃(BO₃) ₄ crystal with low Yb³⁺ doping concentration is better than that with high Yb³⁺ concentration. (© 2003 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Laser‐induced crystal growth of nonlinear optical Ba3Ti3O6(BO3)2 on glass surface

Nonlinear optical Ba₃Ti₃O₆(BO₃)₂ crystals were patterned on the surface of CuO (1 mol%)‐doped 40BaO‐40TiO₂‐20B₂O₃ glass by irradiations of continuous‐wave Nd:YAG (wavelength: λ=1064 nm) and Yb:YVO₄ (λ=1080 nm) lasers. Laser energies absorbed by Cu²⁺ ions were transferred to the lattice system through a nonradiative relaxation process, consequently heating the glass and inducing local crystallizations. For the lines patterned by Yb:YVO₄ laser irradiations with a power of 1 W and a scanning speed of 20 μm/s, a c‐axis orientation of Ba₃Ti₃O₆(BO₃)₂ crystals along the laser scanning direction is proposed from measurements of X‐ray diffraction analyses, polarized optical photographs, polarized micro‐Raman scattering spectra, and azimuthal dependence of second harmonic generations. The laser‐induced crystallization technique is found to be applied successfully for the spatially selective patterning of nonlinear optical Ba₃Ti₃O₆(BO₃)₂ crystals in glass. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Second harmonic generation in Na3Gd2(BO3)3 crystals

Na₃Gd₂(BO₃)₃ crystals with dimensions up to 22 × 20 × 5 mm³has been grown from NaBO₂ flux by the top‐seeded solution growth (TSSG) method for the first time. Differential scanning calorimetry (DSC) result shows that Na₃Gd₂(BO₃)₃ melts incongruently. The infrared spectrum indicates that Na₃Gd₂(BO₃)₃ contains characteristic triangular [BO₃]^3– groups responsible for the nonlinear optical effect. For the as‐grown crystal, the transmittance exceeds 80% in the wavelength range of 315 nm to 2670 nm, and the UV cutoff wavelength is 207 nm. The damage threshold is 0.47 GW cm^–2 at 1064 nm. Moreover, Na₃Gd₂(BO₃)₃ crystal exhibits an optical second harmonic generation effect which is 1.3 times as large as that of KH₂PO₄ (KDP). (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Spectroscopic manifestations of local crystal distortions in excited 4f states in crystals of huntite structure

Optical absorption spectra of YbAl₃(BO₃)₄, TmAl₃(BO₃)₄ and TbFe₃(BO₃)₄ trigonal crystals have been studied in temperature range 2–300 K. Temperature behavior of absorption lines parameters has shown, that during some f-f transitions the local environment of rare earth ions undergo distortions, which are absent in the ground state.     

Single crystals of calcium and strontium phenylphosphonate grown via hydrothermal crystallization

Single crystals of Ca(HO₃PC₆H₅)₂ (1) and Sr(HO₃PC₆H₅)₂ (2) have been obtained via the crystallization of their respective amorphous powders. The amorphous compounds were synthesized by traditional solution routes and were subsequently crystallized at 160°C in a Teflon-lined autoclave containing 1–3 mL distilled water. The resultant single crystals were physically isolated and their structures determined by single crystal X-ray diffraction. The two compounds are isostructural and crystallize in space group C2/c with lattice parameters of a = 31.267(3) ?, b = 5.6185(6) ?, c = 7.7202(8) ?, β = 101.924(2)°; and a = 31.514(4) ?, b = 5.8098(8) ?, c = 7.8218(10) ?, β = 102.063(3)° for the calcium and strontium phenylphosphonate, respectively.     

Neodymium incorporation into YAl-borate crystals in preparation from solutions in molten potassium trimolybdate

The limits of neodymium substitution for yttrium in (Y, Nd)Al₃(BO₃)₄ crystals in preparation from solutions in molten potassium trimolybdate have been studied. The maximum neodymium concentration in the crystals was 72 at.%, this corresponding to the ratio Nd:Y = 1 in the solution. When this ratio exceeds unity, only potassium-neodymium molybdate is formed. The distribution coefficient for neodymium is greater than unity and decreases both with the increasing Nd/Y ratio in the melt and with decreasing growth rate of the crystals. The unit cell parameters change in the series YAl₃(BO₃)₄ NdAl₃(BO₃)₄ in a non-steady manner, this indicating that the structure is inclined to disordering.     

Growth of (Er,Yb):YAl3(BO3)4 laser crystals

(Er,Yb):YAl₃(BO₃)₄ single crystals of optical quality, up to 15 × 10 × 10 mm³ in size, have been grown from a (Er_0.023Yb_0.116Y_0.862)Al₃(BO₃)₄ solution in a Y₂O₃-B₂O₃-K₂Mo₃O₁₀ melt. The initial borate concentration was 17 wt %, and the flux cooling rate increased from 0.08 to 0.12°C/h in the range 1060–1000°C. The physical properties of the single crystals grown are good enough that they can be used as laser elements in systems with diode pumping and radiation near 1.5 μm.     

Growth and dichroic properties of LiBa12(BO3)7F4 crystal

The bulk crystals of LiBa₁₂(BO₃)₇F₄ were obtained from two flux compositions by the top seeded solution growth method. Crystals grown from BaCO₃:BaF₂:H₃BO₃:Li₂CO₃ = 3:3:3:1 charge were found to have a distinct linear dichroism effect at 0.35–0.65 and around 0.73 μm. This suggests application of the material in the production of polarizing filters and attenuators for visible range lasers.     

Rare-earth and lead mixed anionic oxoborates

TheNd_4.5Pb_1.7(VO₄)_0.3(BO₃)O_6.42(I), Tb_4.5Pb_1.6(GeO₄)_0.4(BO₃)O_6.02(II), Dy_4.5Pb_1.68(GeO₄)_0.32(BO₃)O_6.28(III), and Ho_8.66(BO₃)₂(B₂O₅)O₈(IV) crystals were grown by spontaneous crystallization from flux and studied by the methods of X-ray diffraction analysis. The unit-cell parameters are a = 21.946, 21.590, 21.478, and 18.207 Å; b = 3.7881, 3.6565, 3.6333, and 3.6685 Å; c = 16.857, 16.618, 16.544, and 14.024 Å; β = 123.70°, 124.64°, 124.49°, and 119.81°; sp. gr. C2/m; and Z = 4, 4, 4, and 2 for I, II, III, and IV, respectively. In I–III compounds, Pb atoms, together with the atoms of group V, and Pb atoms and Ge atoms occupy the mixed positions. In structure IV, all the five independent Ho positions are occupied only partially.     

Flux crystallization of trigonal GdFe<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)<Subscript>4</Subscript> competing with the crystallization of α-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>

The formation of trigonal GdFe₃(BO₃)₄ crystals in the Bi₂Mo₃O₁₂-B₂O₃-Li₂MoO₄-Gd₂O₃-Fe₂O₃ system was studied. The flux compositions for which GdFe₃(BO₃)₄ is the high-temperature phase with a wide range of crystallization were determined. The features of nucleation of these crystals and their growth near the phase boundary with α-Fe₂O₃ were analyzed. The growth of GdFe₃(BO₃)₄ single crystals involving preliminary nonequilibrium crystallization of α-Fe₂O₃ is described.     

Synthesis, spectroscopic characterization and X-ray structure determination of tetrabutylammonium trans-diamminetetranitrocobaltate(III)

The cobalt(III) complex salt [(C₄H₉)₄N][trans-Co(NH₃)₂(NO₂)₄] has been synthesized in high yield by reacting equimolar quantities of [(C₄H₉)₄N]Br and K[trans-Co(NH₃)₂(NO₂)₄] in aqueous medium at room temperature. The product thus formed has been re-crystallised from acetone-water mixture, in the monoclinic space group P 2₁/n, with cell dimensions a=11.651(3) ?, b=19.005(4) ?, c=11.733(5) ?, β=90.28(3)°. The X-ray structure determination revealed the presence of discrete ions, [(C₄H₉)₄N]⁺ and [trans-Co(NH₃)₂(NO₂)₄]⁻. The central metal ion cobalt(III) in the anion is found in octahedral environment, in trans geometry, while the organic counterion is a quaternary alkylammonium cation. The crystal lattice is stabilized by electrostatic interactions between the cations and anions.Supplementary material Crystallographic data (excluding structure factors) for the structure(s) reported in this paper have been deposited with the Cambridge Crystallographic Data Centre as supplementary publication no. CCDC 291300. Copies of the data can be obtained free of charge on application to CCDC, 12 Union Road, Cambridge CB2 1EZ, UK (fax: (44) 1223 336-033; e-mail: deposit@ccdc.cam.ac.uk.     

Growth and thermal studies on pure ADP,KDP and mixed K1‐x(NH4)xH2PO4 crystals

The investigations on the formation of mixed crystals of ammonium dihydrogen orthophosphate (ADP) and potassium dihydrogen orthophosphate (KDP) i.e. potassium ammonium dihydrogen phosphate, K_1‐x(NH₄)_xH₂PO₄ have been presented in this paper. Pure and mixed crystals of ADP and KDP have been grown by slow evaporation technique from the supersaturated solution at an ambient temperature 26±1 °C for ammonium concentration x in the range 0.0 ≤ x ≤ 1.0 in the case of mixed crystals. Crystal compositions were determined by flame atomic absorption spectroscopy and chemical analysis. The results of the X‐ray analysis of the grown crystals are also reported. Thermogravimetric analysis (TGA) and differential thermal analysis (DTA) were used to study the kinetic process of dehydration and the high temperature phase behaviour. DTA showed the distinct thermal events attributed to dehydration of ADP, KDP and K_1‐x(NH₄)_xH₂PO₄. The results of thermal analysis and chemical analysis are consistent with each other. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Self‐assembly synthesis and structure of mono‐ and di‐nuclear uranyl complex

Mixing the malonate (mal), 4,4′‐bipyridine, UO₂(CH₃COO)₂ · 2H₂O in different solvent condition gets two compounds (bpy)₂(H₂bpy)[UO₂(mal)₂(μ‐H₂O)] · 8H₂O (1) and (H₂bpy)[UO₂(mal)₂] · 2H₂O (2) . Both complexes contain seven‐coordinated pentagonal bipyramidal uranium center. Crystal 1 is mononuclear structure and crystal 2 contains dinuclear [(UO₂)₂(mal)₂(μ₂‐mal)₂]^4‐ subunit. Particularly, Crystal 2 forms the twodimensional supramolecular topology by hydrogen bonds. The sheet constructs from two sorts of chamber, of which the larger one has two water molecular guests. (© 2003 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

A Novel Three Dimensional Organic–Inorganic Hybrid Based Porous Phase: Synthesis and Characterization of Reduced Oxovanadium pyromellitate, [VIV2O2(H2O)2(C6H2(COO)4)]

The hydrothermal reaction of a mixture of VOSO₄ · xH₂O, 1,2,4,5-benzenetetracarboxylic acid (pyromellitic acid) and 0.1 M H₂SO₄ for 72 h at 160 °C gives blue needle like crystals of [V^IV ₂O₂(H₂O)₂(C₆H₂(COO)₄)] in 30% yield. The compound has a porous 3-D extended network structure having a rigid architecture which is held together by the multidentate functionalities of 1,2,4,5-benzenetetracarboxylate ligand. Crystal data for the compound: monoclinic space group C 2/c (No:15), a = 11.756(5) ?, b = 9.645(3) ?, c = 11.822(7) ?, β = 107.10(4)°, Z = 8. The compound constitutes the first example of a fully reduced oxovanadium based solid incorporating the organic ligand. This article consists of synthesis, crystal structure and characterization of [V^IV ₂O₂(H₂O)₂(C₆H₂(COO)₄)].     

Carbonyl Displacement Reaction in Diiron Propane-Dithiolate Complex by Triphenylstibine: Crystal Structure of [Fe2(CO)6-n(SbPh3)n(μ-S2C3H6)] (n = 1 and 2)

Treatment of [Fe₂(CO)₆(μ-S₂C₃H₆)] (1) with triphenylstibine in a 1:1 molar ratio at room temperature in presence of Me₃NO resulted compound [Fe₂(CO)₅(SbPh₃)(μ-S₂C₃H₆)] (2) in 88% yield as red crystals. When the reaction was carried out under a 1:5 molar ratio in presence of Me₃NO, it resulted a monosubstituted compound [Fe₂(CO)₅(SbPh₃)(μ-S₂C₃H₆)] (2) in 63% yield along with a disubstituted compound [Fe₂(CO)₄(SbPh₃)₂(μ-S₂C₃H₆)] (3) in low yield (8%) as red crystals. Reaction of 2 with triphenylstibine in a 1:5 molar ratio under same condition resulted 3 in moderate yield (46%). Compounds 2 and 3 were characterized by elemental analyses, IR, ¹H NMR and ¹³C NMR spectroscopic data. Crystal structures of the compounds were unambiguously determined by single crystal X-Ray diffraction studies. Compound 2 crystalized as monoclinic crystal system with the space group P2₁/c, a?=?9.464(4) Å, b?=?16.902(7) Å, c?=?17.081(7) Å, β?=?101.216(13)° and Z?=?4. Compound 3 was triclinic, space group P-1, a?=?9.552(3) Å, b?=?13.985(5) Å, c?=?16.487(6) Å, α?=?78.372(16)°, β?=?89.976(14)°, γ?=?71.638(11)° and Z?=?2.

Graphic Abstract

Two new diiron propane-1,3-dithiolate complexes, [Fe₂(CO)₅(SbPh₃)(μ-S₂C₃H₆)] (2) and [Fe₂(CO)₄(SbPh₃)₂(μ-S₂C₃H₆)] (3), were synthesized by the displacement of carbonyl groups from [Fe₂(CO)₆(μ-S2C₃H₆)] (1) with triphenylstibine, and the resulting complexes were structurally characterized.

Solid state molecular structure of compound 2 (left) and compound 3 (right)

     

Crystal Structure of pyridinium isopolymolybdate (C5H6N)2n[Mo4O13]n

Synthesis and crystal structure are described for pyridinium isopolymolybdate of chemical composition (C₅H₆N)_2n[Mo₄O₁₃]_n. The crystals are triclinic, space group P1, with the following unit‐cell parameters: a =8.2695(11) Å, b =10.544(4) Å, c =11.177(4) Å, α = 71.76(5)°, β = 89.68(3)°, γ = 78.79(3)°, V =906.4(4) ų, Z = 2 (chemical formula (C₅H₆N)₂[Mo₄O₁₃]), D _calcd = 2.755 g·cm^–3. Crystal structure was solved by Patterson methods and refined to a final R value 0.085 for 4045 independent reflections. The studied compound, considered in analogy to triclinic (NH₄)₂Mo₄O₁₃ as pyridinium polyoctamolybdate, is proposed to be better described as pyridinium isopolytetramolybdate (C₅H₆N)_2n[Mo₄O₁₃]_n. It seems that the proper coordination number of molybdenum (VI) ions is five, resulting in pyramidal coordination polyhedra [MoO₅]. Coordination polyhedra joined by common edges form tetramolybdate monomeric unit [Mo₄O₁₃]. The mers are connected by oxygen bridges Mo ‐ O ‐ Mo into infinite ribbon chains. Each two infinite chains are hold together by weaker intermolecular interactions. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Contribution to the study of elastic properties of KGd(WO4)2:Er3+ single crystals by Brillouin spectroscopy

In this paper we present the study of the acoustic phonons propagating in Er³⁺‐doped KGd(WO₄)₂ single crystals by Brillouin spectroscopy. For the investigated crystals the velocities of the longitudinal and transverse acoustic phonons [100], [010], [001], [101] and [110] have been determined. Moreover, the values of the elastic constants: C₂₂, C₄₄ and C₆₆ of Er³⁺‐doped KGd(WO₄)₂ single crystals have been estimated. It was revealed that the presence of the Er³⁺‐ions in KGd(WO₄)₂ crystals, for the used doping concentration 1 at% does not influence their elastic properties. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Structural and spectroscopic study of Mg13.4(OH)6(HVO4)2(H0.2VO4)6

Single‐crystals of the polar compound magnesium hydrogen vanadate(V), Mg_13.4(OH)₆(HVO₄)₂(H_0.2VO₄)₆, were synthesized hydrothermally. It represents the first hydrogen vanadate(V) among inorganic compounds. Its structure was determined by single‐crystal X‐ray diffraction [space group P 6₃mc, a = 12.9096(2), c = 5.0755(1) Å, V = 732.55(2) ų, Z = 1]. The crystal structure of Mg_13.4(OH)₆(HVO₄)₂(H_0.2VO₄)₆ consists of well separated, vacancy‐interrupted chains of face sharing Mg2O₆ octahedra, with short Mg2—Mg2 distances of 2.537(1) Å, embedded in a porous magnesium vanadate 3D framework having the topology of the zeolite cancrinite. All three hydrogen positions in the structure were confirmed by FTIR spectroscopy. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Elastic properties of KGd(WO4)2:Ho3+ single crystals studied by Brillouin spectroscopy

The analysis some of the acoustic phonons propagating in pure and Ho³⁺‐doped KGd(WO₄)₂ single crystals in the GHz frequency range by Brillouin scattering method has been presented. For investigated crystals the velocities of the longitudinal and transverse acoustic phonons [100], [010], [001], [101], [101] and [110] have been determined. Moreover, the value of elastic constants C₂₂, C₄₄ and C₆₆ of pure and Ho³⁺‐doped KGd(WO₄)₂ single crystals have been estimated. It was revealed that the presence of the Ho³⁺‐ions in KGd(WO₄)₂ crystals, for the used doping concentration 1 at% and 8 at%, does not influence their elastic properties. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Crystal structures of two monoamine-coordinated zinc complexes obtained via solid-vapor reaction

The solid-vapor reaction properties of [Zn(p-NH₂C₆H₄SO₃)₂(H₂O)₂] _n and alkyl monoamines were investigated. Two of the resulting complexes, [Zn(C₂H₅NH₂)₄](p-H₂NC₆H₄ SO₃)₂ and [Zn(n-C₃H₇NH₂)₄](p-H₂NC₆H₄SO₃)₂, grew into single crystals in situ during the solid-vapor reaction process and their structures were characterized by single-crystal structural analysis.