Single Crystal Growth and Luminescent Properties of Na_5Eu(WO_4)_4

The single crystal growth of stoichiometric host luminescent crystal Na_5Eu(WO_4)_4 has been investigated.Using Na_2WO_4 as a flux,the optimum conditions to grow a pure single crystal by flux-slow-cooling methodhave been determined.A high optical quality single crystal of dimention 4.5 mm has been grown,which is thelargest one as we know so far.The micro-hardness of Na_5Eu(WO_4)_4 single crystal is 3.46×10~3 MPa.Itsrefractive index is 1.81 in white light wavelength region and the specific gravity is 5.65 g/cm~3.The fluorescentand excitation spectra have been determined and the reason of the fluorescent quench of ~5D_2 and ~5D_1 to ~7F_jof Eu~(3 )can be explained as multi-phonon non-radiation transition.     

Crystal Structure and Characterization of Neodymium Phenylacetate Hydrate

The crystal structure of Nd(ph-CH_2COO)_3H_2O has been determined by X-ray diffraction technique.Thecrystal behmgs to orthorhombic system with space group P_(na)2_1,cell parameters a=0.7983(1)nm,h=1.3957(1)nm,c=2.0282(2)nm;V=2.2598(15)nm~3,Z=4.The Mechanism and enthalpy changes ofthermal decomposition reaction of the title complex have been studied by TG-DTG-DTA and DSC.     

Synthesis of the Early Lanthanide Complexes[Li(DME)_3][MeCpLn(NPh_2)_3](Ln=La,Pr,Nd)and X-Ray Crystal Structure of La Complex

The reaction of MeCpLnCl·2LiCl·nTHF with 2 equivalent of LiNPh_2 in THF,hexane andtoluene mixture solution gives the new complex[Li(DME)_2][(η~5-MeCp)Ln(NPh_2)_3](Ln=La,Pr,Nd)byextraction with DME.They have been characterized by elemental analysis,IR and NMR.The La complexcrystallizes in the monoclinic space group P2_1/c with α=1.8335(6)nm,b=1.6576(5)nm,c=1.7461(6)nm,β=96.04°,V=5.277 nm~2,Z=4,D_c=1.26g·cm~(-3),R=0.057 and R_w=0.048(1≥2.5σ(I_o))for 3378 reflec-tions.The complex consists of a pair of a cation and an anion.La~(3+) is coordinated by onemethylcyclopentadienyl and three diphenylamidos to form six-coordinate pseudotetrahedron with the meanLn-N and La-C(ring)distances of 0.2459(8)and 0.2843(11)nm,respectively.     

Crystal Structure of a Heteronuclear Complex of Erbium-Yttrium and Glycine [ErY(GIy)_6(H_2O)_4] (ClO_4)_6·5H_2O

The title complex [ErY(Gly)_6(H_2O)4](ClO_4)_6·51H_2O has been synthesized.Its crystal structure has beendetermined by X-ray diffraction method.The crystal is triclinic with space group P.The unit cell parametersare as follows:a=1.1518(4) nm,b=1.4105(7) nm,c=1.5530(6) nm,α=96.61(3)°,β=102.74(3)°,γ=105.70(3)°,V=2.3277(17) nm~3,Z=2,D_(calc)=2.091 g/cm~3.The structure has been refined to a final R of0.0785.The crystal-is an infinite chain complex,in which four carboxyl groups from glycine molecules bridge theEr~(3+) and Y~(3+) ions,and the other two carboxyl groups bridge two adjacent Er~(3+) or Y~(3+) ions.     

Structure and Luminescent Enhancement Effect of Na_5Eu(MoO_4)_4 by Doping(WO_4)~(2-)

The luminescent enhancement effect of Na_5Eu(MoO_4)_4 by doping(WO_4)~(2-) has been studied.When the value x in Na_5Eu(Mo_(1-x)W_xO_4)_4 is in 0相似文献   

Studies on Lattice Vibrational Modes of Na_5Eu(WO_4)_4 Single Crystal by Raman Spectrum

Raman and infrared spectra of host luminescent crystal Na_5Eu(WO_4)_4 in several different geometric con-figurations have been investigated.The symmetrical species of lattice vibrational modes of the crystal have beenanalysed by means of the site group analysis method of group theory.The experimental vibrational modes havebeen assigned to A_g,B_g,E_g,A_u and E_u of crystal factor group C_(4h).Because the energies of stretchingvibrational modes of(WO_4)~(2-)ion groups are very high(in the range of 755～940 cm~(-1)),multiphononnonradiative transitions of ~5D_2→~5D_1 and ~5D_1→~5D_0 in Eu~(3 )will occur.So it causes Eu~(3 )ions inNa_5Eu(WO_4)_4 to emit ~5D_0→~5F_j(j=1,2,3,4)emissions mainly at room temperature and the emission light ofNa_5Eu( WO_4)_4 has high red colour purity.     

Crystal structure and phase relations of Pr_2Fe_(14)B-La_2Fe_(14)B system

The crystal structure and phase relations of the Pr_2Fe_(14)B-La_2Fe_(14) B system were investigated by X-ray powder diffraction(XRD), differential scanning calorimetry(DSC) and scanning electron microscopy(SEM) equipped with energy dispersive X-ray spectroscopy(EDS). The crystal structure parameters were determined by full-profile Rietveld refinements. The results revealed that all alloys of(Pr_(1–x)La_x)_2Fe_(14)B crystallized the Nd_2Fe_(14)B-type structure with the space group P4_2/mnm and formed a continuous solid solutions between x=0.0 and 1.0. The lattice parameter a, c, unit-cell volume V and c/a ratio increased linearly with the La concentration. Determined by thermogravimetry analysis, the Curie temperature(T_C), phase transition temperature and melting temperature of(Pr_(1–x)La_x)_2Fe_(14)B decreased linearly upon the La content. Based on the results of DSC measurements and X-ray powder diffraction examinations, the phase diagram of the Pr_2Fe_(14)B-La_2Fe_(14) B system was built up.     

Studies on NaLn(WO_4)_2 Single Crystals(Ln=La,Pr,Nd)

The crystals of NaLn(WO4)_2(Ln=La,Pr,Nd)are grown from a melt of LiCl-Na_2WO_4 flux by slowcooling method.The chemical analysis data show that the crystals are NaLa(WO_4)_2,NaPr(WO4)_2 andNaNd(WO_4)_2 respectively.The structures of the crystals are ascertained that they belong to scheelite structureof the tetragonal system with a space group of 14_1/a.The lattice parameters of the crystals have beencalculated.It is found that the cell volume of NaLn(WO_4)_2 crystals decrease with a decrease of Ln~(3 )radius.The bond distances and their angles in NaLa(WO_4)_2 and NaNd(WO_4)_2 are given.It is found that inaccordance with the decrease of ionic radii of Ln~(3 )due to increase of atomic number,the bond distances betweenLn-O,Ln-Ln and W-O decrease regularly.The infrared spectra of NaLn(WO_4)_2 are measured.Thetetrahedra characteristic absorptions of WO_4~(2-)are shown.The sensitization of host lattice is observed from theexcitation and fluorescent spectra of NaLa(WO_4)_2 and NaPr(WO_4)_2.     

Synthesis and Spectroscopic Characterization of Compounds of Lanthanide-2,4-Pentanedionates with Pyridine

Compounds of the formula [Ln(pd)_3(py)_2] where Ln=La～Yb and Y except Pm and Tin,Hpd (=2,4-pentanedione) and py (=pyridine) have been synthesised and characterised by physical and spectral studies.Pyridine is coordinated in all the compounds.The covalency parameters β,b~(1/2),δ and η indicate at least somecovalency in these compounds.The compounds have been checked for their use as NMR shift reagents usingcholesterol as substrate.Eight coordinate compounds increase their coordination number when added to thesubstrate.     

Study on the Separation of Rare Earths with the Method of H(DEHP)-Extraction Chromatography

Separation of rare earths was investigated by extraction chromatography where H(DEHP)wasused as a stationary phase,while HCl and H_2SO_4 solutions as a mobile phase.The average separation fac-tors of rare earths,β_(HCl) and β_(H_2SO_4),are 3.79 and 4.57.respectively.The β_(La)~(Ce) in HCl and H_2SO_4 systems areas high as 28.5 and 26.3,respectively.The elution acidity in the study can be down to one tenth and one four-teenth of that in HEH(EHP)system.     

Influence of reaction parameters on the luminescence properties of monodisperse NaGd(1−x−y)(WO4)2:xEu3+,yTb3+ phosphor by molten salt synthesis

Eu~(3+) activated and Eu~(3+), Tb~(3+) co-activated monodisperse sodium double tungstates NaGd(WO4)2 phosphors were prepared by molten salt method at 750 ℃ for 10 h using NaCl as a flux. The crystal structure and morphology of the as-synthesized phosphors were measured by XRD and SEM, respectively. The photoluminescence properties were characterized by PL spectra, decay lifetime and CIE. The presence of NaCl plays an important role in the morphology and luminescence properties. In this work,NaCl and one of the raw material Na_2 CO_3 in a certain proportion will form a low eutectic salt to decrease the reaction temperature and benefit the formation of monodisperse NaGd(WO_4)_2 crystals. The color of Eu~(3+) and Tb~(3+) co-doped NaGd(WO_4)_2 phosphors can be tuned from creamy white to orange, red and green by adjusting the doping concentration of rare earth ions, since the emission contain the broad blue-green emission origin from NaGd(WO_4)_2 host and characteristic red and green emission origin from Eu~(3+) and Tb~(3+) ions. The electroluminescent spectra and CIE measurement shows that the LED device with NaGd_((1-x))(WO_4)_2:xEu~(3+)(x = 0.24) phosphor can be excited by 365 nm and 380 nm LED chip, and their CIE coordinate is(x = 0.45, y = 0.45) and(x = 0.36, y = 0.37), Ra is 80.3 and 86.3, T_c is 3196 and4556 K, respectively. As a single-component phosphor, NaGd(WO_4)_2:Eu~(3+),Tb~(3+) have potential application in UV-pumped WLEDs.     

Crystal growth,structure and laser performance of a new Yb~(3+):KBaY(MoO_4)_3 crystal

A Yb~(3+):KBaY(MoO_4)_3(Yb3+:KBYM) crystal with dimensions of 51 mm × 27 mm x 10 mm was successfully grown by the TSSG method.The characteristics of the crystal structure and probability of good optical properties were analyzed.The absorption and emission spectra of Yb3+:KBYM crystal exhibit broadened bands,with the maximum absorption cross-sections of 1.17 x 10~(-20),1.44 ×10~(-20) and 1.37 x 10-20 cm~2 at976 nm for X-,Y-and Z-polarizations,respectively.The corresponding absorption FWHMs are as wide as 77,46 and 55 nm.The well-known re-absorption effect of Yb3+in the crystal is discussed.Two methods,the Fiichtbauer-Ladenburg method(FL) and reciprocity method(RM) were adopted to compute the emission cross-sections and results show a certain discrepancy but the errors are allowable.The laser potentiality of the Yb3+:KBYM crystal was also evaluated by calculations of minimum inversion fraction β_(min),saturation pump intensity I_(sat),the minimum pump intensity I_(min) and gain cross-sections spectra.Laser experiment was carried out and Watt-level continuous wave laser has been realized.Results indicate that the Yb~(3+):KBYM crystal with a disordered structure may be a potential laser media that can be used to generate tunable and ultrashort pulse laser emissions with high quality beam.     

Crystal Structure of{[(μ_2-Cl)(C_5H_5)Sm(μ_2-Cl)]_2(μ_3-Cl)(μ_4-O)Sm(μ_2-Cl)·THF}_2~(2-)·[Li(DME)_2·Li(THF)_2·DME]~(2 )·DME

The crystal structure of title complex has been determined by the method of X-ray single crystaldiffraction.The crystal belongs to monoclinic space group C_(2/c)with the unit parameters a=2.8907(7),b=2.0431(5),c=1.5723(3)nm;β=115.67(2)°.The unit volume V is 8.36924(348)nm~3;Z=8,Dc=1,82g·cm~(-3),μ(MoK_α)=46.4cn~(-1); F(000)=4416.The final R is 0.083,Rw 0.088.The title complex con-sists of two univalent cations and one divalent anion.The anion has a cluster structure including six Sm~(3 ).Coordination numbers of all six Sm~(3 )are eight,but their surroundings are different from each other.Two ofthem are decahedral array,and the others are octahedral array f the centroid of each pentacyclodienyl ring istaken as one point.     

Hydrothermal synthesis and structural studies of a new coordination polymer of lanthanum(Ⅲ) with benzene-1,2,4,5-tetracarboxylic acid and 4,4''-bipyridine

A new lanthanum complex formulated as { (bpyH2)[La(btc)(H2O)4(NO3)]·2H2O }n (1) (btcH4=benzene-1,2,4,5-tetracarboxylic acid; bpy=4,4'-bipyridine) was hydrothermally synthesized. The complex was characterized by FT-IR spectroscopy, elemental analysis and X-ray diffraction. X-ray crystal structural analysis revealed that the compound belonged to the monoclinic space group C2/c with cell parameters a= 1.42806(7) nm, b=1.10258(5) ran, c=-1.60333(8) nm and β=101.9400(10)°. The complex was polymeric with La<Ⅲ atoms linked by four O atoms from two carboxylate groups of one benzene-1,2,4,5-tetracarboxylate. The LaⅢ atom was ten coordinated in a distorted tetracapped trigonal prism. In the crystal structure, a wide range of noncovalent interactions consisting of hydrogen bonding (of the types of O-H…O, N-H…O and C-H…O) and ion pairing interactions connected the various components into a supramolecular structure.     

Synthesis and thermal behavior of [Li(thf)_3(μ-Cl)La{N(SiMe_3)_2}_3] and its investigation as spin-coating precursor for lanthanum-based layer formation

The lanthanum(Ⅲ) complex [Li(thf)_3(μ-CI)La{N(SiMe_3)_2}_3](3) was obtained by the reaction of LaCl_3 with three equiv of Li[N(SiMe_3)_2]_3 in a tetrahydrofuran solution. The molecular structure of 3 in the solid state was characterized by a tetracoordinated anionic lanthanide(Ⅲ) amide in form of an adduct with LiCl(thf)_3 as evidenced by single crystal X-ray structure analysis. In order to study the suitability of 3 as a precursor for the deposition of La_2O_3/LiLaSiO4 by thin layer deposition techniques,its thermal behavior was investigated by thermogravimetry(TG) and TG-MS-coupled studies. TG studies show a two-step decomposition process, whereby volatile decomposition products can be detected during the second decomposition step. TG measurements under an atmosphere of oxygen produced La_2O_3, Calcination processes of 3 under ambient atmosphere for 10 h at 1000 ℃ gave La_2O_3 and LiLaSiO_4,which was confirmed by PXRD studies. Metal-organic 3 was applied as spin-coating precursor for La_2O_3 thin film formation giving the as-deposited layers nearly crack-free.     

STUDIES ON RARE EARTH COMPLEXES WITH CROWN ETHERS ⅩⅧ——Synthesis,Characterization and Crystal Structure of[Sc(NO_3)_3(H_2O)_2]·(15-Crown-5)

The single crystal of the complex [Sc(NO_3)_3(H_2O)_2]·(15C5) has been prepared in acetonitrile.Thenew complex has been characterized by elemental analysis,IR spectra,solubility and molar conductancemeasurements.The structure of the complex is determined by single crystal X-ray diffraction analysis.     

Behavior of sulfate in preparation of single light rare earth carbonate by Mg(HCO_3)_2 precipitation method

The precipitation of the water-leaching solution of Baotou mixed rare earth(RE) concentrate roasted with sulfuric acid using ammonium bicarbonate for producing RE carbonate produces a mass of ammonia-nitrogen wastewater because of the relatively low solubility of rare earth sulfate.To solve the serious problem of ammonia-nitrogen pollution,new precipitators need to be developed urgently so as to meet the requirements of environmental protection and impurities content of the product(SO_4~(2-)1.8 wt% in RE carbonates products).In this paper,we studied the effects of feeding modes on the behavior of SO_4~(2-) during the preparation of light RE carbonate(RE=La,Ce,Pr,Nd) from their sulfate solutions using Mg(HCO_3)_2 as a precipitant.The results indicate that the contents of SO_4~(2+) in the La and Ce precipitates using positive feeding mode exceed 16 wt% because of the formation of La2(CO_3)_(2.15)(-SO_4)_(0.85)·4 H_2 O and Ce2(CO_3)_(2.15)(SO_4)_(0.85)·3 H_2 O,while those of the Pr and Nd precipitates are 4 wt%-5 wt%since they exist in the form of n-carbonate.The precipitates prepared using synchronous feeding mode are all RE carbonate with only 4 wt%-5 wt% of SO_4~(2-) enclosed in the precipitation.The content of SO_4~(2-) in the RE carbonate obtained using reverse feeding mode is the lowest.Among them,the content of SO_4~(2-) in La precipitate is only 1.40 wt%.Both synchronous and reverse feeding modes can effectively reduce the content of SO_4~(2-)in RE carbonate,which provides theoretical guidance for the preparation of qualified light RE carbonate products by Mg(HCO_3)_2 precipitation method.     

Mechanism of Thermal Decomposition of Rare Earth Acetate Hydrates

The mechanism of thermal decomposition of rare earth acetate hydrates(Ln(Ac)_3·nH_2O,n=5,forLn=La;n=4,for Ln=Pr→Lu,Y,except Pm)has been studied by TG-DTG,DSC,infrared spectra,X-raydiffraction and chemical analysis.The thermal decomposition reaction consists of two stages,one is dehydrationand the other one is decompostion.The final product is oxide.It has been found that the temperature of pro-ducing anhydrous acetates decreases with increasing atomic number of rare earth elements.The activation ener-gies for dehydration and decomposition reaction of rare earth acetate hydrates have been calculated byFreeman-Carroll and Kissinger method.The dependence of activation energy Jor dehydration reaction on theatomic number of rare earth elements shows“inclined‘W’effect”.The enthalpy changes for dehydration anddecomposition reaction have been determined.     

Growth,structural, spectral and high-power continuous-wave laser operation of Yb_(0.11)Gd_(0.89)COB crystal

A Yb_(0.11)Gd_(0.89)Ca_4O(BO_3)_3 crystal with new composition was grown by the Czochralski method. The crystal structure was measured and analyzed. The unit-cell parameters of the Yb_(0.11)Gd_(0.89)COB were calculated to be a=0.8089(7) nm, b=1.5987(6) nm, c=0.3545(8) nm, β=101.22o. The absorption and fluorescence spectra were measured. The maximum absorption cross-section of Yb_(0.11)Gd_(0.89) COB crystal was 0.79×10~(–20)cm~2, which occurred at 976 nm with Y polarization. The emission cross-section at 1027 nm was calculated to be 0.33×10~(–20) cm~2. The radiative lifetime trad was calculated to be 2.74 ms. The Stark energy-level diagram of Yb~(3+)in the Yb_(0.11)Gd_(0.89)COB crystal field at room temperature was determined. The ground-state energy level ~2F_(7/2) splitting was calculated to be as large as 1004 cm~(–1) and the zero-line energy was 10246 cm~(–1). A maximum output power of 9.35 W was achieved in continuous-wave(CW) mode, with the slope efficiency being 42.1%. Chemical etching experiment revealed that the dominating imperfections in the studied Yb_(0.11)Gd_(0.89) COB crystal were dislocations and sub-grain boundaries. The existence of crystal defects could cause light scattering, and degrade laser output efficiency. The influence of crystal defects on laser properties was discussed.     

Binuclear Lanthanide Complexes Containing SodiumSyntheses and Crystal Structure of (C_5Me_5)_2Nd(μ-Cl)_2Na(DME)_2 and (C_5Me_5)_2Nd(μ-OCH_3)_2Na(DME)_2

The reaction of NdCl_3 with NaC_5Me_5 generates a novel complex (C_5Me_5)_2Nd(μ-Cl)_2Na(DME)_2 (1).Then (1) reacts with 1 mol ratio Na and a little methyl-naphthalene generating another novel complex(C_5Me_5)_2Nd(μ-OCH_3)_2Na(DME)_2 (2).Complex (1) belongs to orthorhombic crystal system,space groupPbn2_1 with a=1.2635(3) nm,b=1.6127(5) nm,c=1.6543(4J nm,V=3.371(2) nm~3,D_c=1.36 gcm~(-3) andZ=4.The central metal Nd is coordinated by two C_5Me5 ring centroids and two μ-chlorine atoms forming adistorted tetrahedron.The crystal of complex (2) is monoclinic,space group C2/n with a=1.7482(5) nm,b=1.3260(4) nm,c=1.6406(7) nm,β=109.39(3)°,V=3.5874(1) nm~3,D_c=1.26 gcm~(-3) and Z=4,Twofive-membered ring centroids and two p-oxygens of OCH_3 form a distorted tetrahedron around the centralneodymium ion.