THE CRYSTAL STRUCTURE OF RARE EARTH COMPLEX WITH AMINO ACIDS Ⅱ The Crystal Structure of Gtutamate Comptex of Erbium Perchtorate

The crystat structure of {[Er;（L—Glu）;（H;O）;]（ClO;）;·3H;O);has been studied by X-ray diffraction. The crystal is monoctinic with space group P2;and cell parameters a=19.987（3） , b=16.505（3） , c=11.040（2） , β=104.69（1）;, V=3538（1） , Z=2, Dc=2.29 g. cm;, μ=53.2 cm;, F（000）=2384. The asymmetric unit contains two complex motecules and four centre ions. Each erbium （Ⅲ） is coordinated by five oxygen donors from four different glutamates and four oxygen donors from the aqua ligand to form a nine coordination potyhedron. The mean distances of Er—0 （carboxylate） and Er—Ow are 2.439 and 2.41 respectivety. The finat R and Rw are 0.043 and 0. 058, respectivety.

Phase Behavior and Crystal Structure of Perovskite-Type Rare Earth Complex Oxides

Several compounds of rare earth complex oxides containing manganese and titanium were synthesized in Ar, and their crystal structures were analyzed by powder X-ray diffraction data and Rietveld method. Structures of A0.67Ln0.33 Mn0.33Ti0.6703（A = Ca or Sr and Ln = rare earth） were found to have orthorhombic symmetry with the space group Pnrna, and their interatomic distances and bond angles were obtained. This space group was also derived from electron microscopic study. Electrical conductivity of Cao.67Ln0.33Mn0.33Ti0.6703 for several rare earth elements showed a semiconducting property with the activation energy of 0.4 eV. Some of these compounds of the strontium system show the antiferromagnetic properties below 10 K.

Syntheses,Crystal Structures and Kinetic Mechanisms of Thermal Decomposition of Rare Earth Complexes with Schiff Base Derived from o-Vanillin and p-Toluidine

Three complexes, [Pr（NO3）3（HL）2] （1）, [Nd（NO3）3（HL）2] （2） and [Er（NO3）3（HL）2] ·0.5H2O （3）, were synthesized from the reaction of a Schiff base ligand 2-[ （4-methylphenylimino）methyl ]-6-methoxyphenol （C15 H15 NO2, HL） with Ln（NO3）3·6H2O （Ln = Pr, Nd, Er）. Characterization by single-crystal X-ray diffraction technique, elemental analysis, molar conductance, FT-IR, UV-Vis, ^1H NMR and thermal analysis shows the title complexes are neutral molecules where the central Ln（ Ⅲ） ion is ten-coordinated in biapical anti-hexahedron prism geometry, with four oxygen atoms of the phenolic hydroxy and methoxy groups in the two bidentate Schiff base ligands and six oxygen atoms provided by the three bidentate NO3 - anions. Additionally, the kinetic mechanism of thermal decomposition of complex 3 was determined with a TG-DTG curves by both integral and differential methods. The functions of thermal decomposition reaction mechanism and the equation of kinetic compensation effect were obtained.

Synthesis and crystal structure of a 1D chainlike rare earth coordinated tungstogermenate:[(CH_3)_4N]_(1.50)H_(3.50)[Gd(GeW_(11)O_(39))(H_2O)_2]·2.5H_2O

AID zigzag polyoxometalate [（CH3）4N]1.50H3.50[Gd（GeW11O39）（H2O）2]·2.5H2O （1） was synthesized by reaction of the monova- cant polyanion [α-GeW11O39]^8- with Gd^3＋ ions in aqueous solution and characterized by IR, UV spectra, ICP, and X-ray crystallography. X-ray single-crystal structural analysis indicated that the title compound crystallized in a monoclinic lattice, C2/c space group with α= 2.8201（5）, b=2.2885（3）, c=2.4033（4） nm, β=123.875 （2）°, V=12.878（4） nm3, Z=8, R1=0.0623, wR2=0.1287. The solid-state structure of the title compound displayed an infinite one-dimensional arrangement built up of [α-GeW11O39]^8- polyanions connected by Gd^Ⅲ cations.

Synthesis, Crystal Structure and Characterization of a One-dimensional Supramolecular Rare Earth Complex of N-(6-(4-Methylpyridinyl))ketoacetamide

A one-dimensional （1D） supramolecular rare earth complex [Nd（NO3）2L2-（C3H6O）][NdL（NO3）4]} （L=N-（6-（4-methylpyridinyl））ketoacetamide） has been prepared and characterized by elemental analysis, IR and electronic spectroscopy, and single-crystal X-ray diffraction. The crystal crystallizes in the triclinic system, space group P1^- with a=0.9146（6）, b=1.2581（8）, c=2.2316（14） nm, α=99.352（10）,β=97.209（9）, γ=103.935（9）°, V=2.422（3） nm3, Dc=1.776 g/cm^3, C33H42N12Nd2O25, Mr=1295.27, Z=2, F（000）=1288, μ=2.217 mm-1, R=0.0508and wR=0.1046 for 5173 observed reflections （I 〉 2σ（I））. In the structure of the title complex,one-dimensional supramolecular double-chains are formed by intermolecular hydrogen bonding interactions.

Syntheses aod Crystal Structures of Rare Earth Complexes with Adamantanecarboxylic Acid, [LnL_3(HL)(H_2O)]_2·2EtOH·2H_2O (Ln=Nd (1), La (2))

The title complexes （LnL3 （HL） （H2O） ]2· 2EtOH·2H2O （Ln= Nd （1）, La （2）, HL=adamantanecarboxylic acid） were prepared and determined by single-crystal X-ray diffraction. Both complexes crystallize in triclinic system with space group P 1^-, cell parameters are： complex （1） a = 1.0556（2） nm, b =1.4913（3） nm, c = 1.4920（3） nm, a = 106.26 （3）°, β=93.51（3）°, γ=97.23（3）°, V=2.2253 （5） nm^3, Dcal=1.409 g · cm^-3, Z = I , F （ 000 ） = 990, μ（Mo Kα） = 1. 225 mm^-1, M, = 1884.50; complex （2） a = 1.0453（2） nm, b = 1.4971（3）nm, c = 1.5052（3） nm, α = 106.07（3）°, β =93.58 （3）°, γ=97.56（3）°, V=2.2391（5）nm^3, Dcal= 1.397 g·cm^-3, Z = 1, F（000） =984, μ（Mo Kα） = 1.015 mm^-1, Mr= 1877.88. The final R and wR are 0. 0396 and 0. 1062 for 8589 （1 ≥ 2σ （I）） observed reflections for complex （1）, 0.0505 and 0. 1344 for 8417 （ 1 ≥ 2σ （1） ） observed reflections for complex （2）, respectively. The crystals are consisted of a binuelear molecule. The coordination geometry of the Ln（ Ⅲ ） ion can be described as trieapped trigonal prism.

Preparation and Crystal Structure of a Rare-earth Salt Based on the Decavanadate (V_(10)O_(28)^(6-)): [Y(H_2O)_8]_2[V_(10)O_(28)]·9H_2O

The salt, [Y（H2O）8]2[V10O28]·9H2O, contains two discrete water-groups coordinated Y（Ⅲ） cations, an isopoly complex ion, decavanadate （V10O28^6-） and nine additional water molecules, which are combined together by static electric forces and hydrogen bonds. The y^3＋ is eight-coordinated with a square antiprism geometry. The single-crystal X-ray analysis reveals that the crystal crystallizes in triclinic, space group P1^- with a = 9.1454 （18）, b = 10.007（2）, c = 12.772（3） A°, α= 68.86（3）, β = 77.50（3）, γ= 89.23（3）°, V= 1061.7（4）A°^3 and Z= 1.

Crystal structure and infrared spectrum of thallium holmium polyphosphate, TlHo(PO_3)_4

Crystals of thallium-holmium polyphosphate T1Ho（PO3）4 were grown by flux method technique and characterized by single crystal X-ray diffraction. Structure of T1Ho（PO3）4 was solved for the first time, and it crystallized in the monoclinic P21/n space group with the following unit-cell dimensions： a=1.02225（3） nm, b=0.88536（2） nm, c=1.09541（4） nm, β=105.888（1）°, V=0.95354（5） nm^3 and Z=4. The crystal structure was solved from 2174 independent reflections with final R1（F^2）=0.0442 and Rw（F^2）=0.0861 refined with 164 parameters. The atomic arrangement could be described as a long chain polyphosphate organization. Holmium atoms had eightfold coordination. The structure of T1Ho（PO3）4 consisted of HoO8 polyhedra sharing oxygen atoms with phosphoric group PO4. Infrared spectrum was investigated at room temperature in the frequencies range, 350--4000 cm^-1, showing some characteristic vibration bands of infinite chain structure of PO4 tetrahedra linked by bridging oxygen.

Synthesis and Structures of A Series of Novel Rare Earth Transition Metal Sulfates

Seven new rare earth transition metal sulfates were synthesized by hydrothermal reactions under conditions slightly above the critical point of water. Their crystal structures were determined from single crystal X-ray data. The compositions of the new compounds can be represented by two general formulae ： REM （OH） 3 （SO4） and RE2M （OH） 3 （SO4） 2F （H2O） with RE = Gd, Tb, Dy ; M = Ni, Cu. Three different crystal structure types were found for the formula REM （OH） 3 （SO4）. The structures of the new compounds all feature infinite chains of REOn coordination polyhedra, which are connected to chains of CuO6 or NiO6 octabedra. The limited size range of the rare earth cations observed in these compounds is most likely because of interactions between the octabedral chains and the chains of REOn polyhedra. The new compounds are closely related to the known yttrium transition metal sulfates.

Theoretical elucidation of rare earth extraction and separation by diglycolamides from crystal structures and DFT simulations

Diglycolamides(DGAs) show excellent application prospects for the extraction and separation of rare earth metals from highly radioactive liquid wastes and rare earth ores.The extraction ability of DGAs for rare earth ions in nitrate or chloride media increases with increasing atomic number of the rare earth metal.To understand the origin of this phenomenon,three binuclear crystals [Ln(TEDGA)_(3)][Ln(NO_(3))_(6)] of N,N,N’,N’-tetraethyldiglycolamide(TEDGA) with rare earth ions La(Ⅲ),Pr(Ⅲ) and Eu(III) were prepared and characterized crystallographically.The three complexes belong to the triclinic crystal system,P-1 space group.The bond lengths of Ln-O_(amide) are significantly shorter than those of Ln-O_(ether) in the same crystal.The Ln-O_(amide) and Ln-O_(enher) bond lengths gradually decrease with increasing atomic number of the rare earth ion.The dihedral angle formed by TEDGA and metal ions through the tridentate coordination gradually increases with increasing metal ion atomic number,tending toward the formation of sizeable planar coordination structures for the most massive rare earth ions.The structures of the compounds formed by the extractant and metal ion were optimized by means of DFT simulations.We find that the interaction between TEDGA and the rare earth ion is dominated by electrostatic interaction by analyzing binding energy,WBIs,Mulliken charge,natural electron configurations,and molecular orbital interaction.The covalent component of the Ln-O bonds of the complexes increases with increasing metal atomic number.The observed increase in extraction and separation capacity of diglycolamides for rare earth ions with increasing atomic number might be due to the formation of two fivemember rings by one tridentate ligand.The rare earth ions with large atomic numbers tend to form planar structures with large dihedral angles with DGA ligands.

Synthesis, Structure and Luminescent Properties of Three 1D Chain Rare Earth Complexes

Three 1 D chain coordination polymers [Ln(pydc)2(H2 O)2]n·n Him(Ln = Dy(1), Gd(2), Sm(3), H2 pydc = pyridine-2,5-dicarboxylic acid, Im = imidazole), were solvothermally synthesized by the reaction of pyridine-2,5-dicarboxylic acid(H2 pydc), Ln(Ⅲ) salts and imidazole. They have been characterized by X-ray single-crystal diffraction, IR spectra, TGA analysis and elemental analysis. Structural analyses revealed that complexes 1~3 have similar 1 D chain structures and belong to P1 space group. It is noteworthy that complexes 1~3 exhibited excellent thermal stability and no weightlessness below 117 ℃. Meanwhile, 1 and 3 show characteristic fluorescence of corresponding lanthanide metal ions in solid state at room temperature.

Synthesis and Crystal Structure of Rare Earth Metal Chlorides Bearing Bridged-lndenyl Ancillary Ligand

Two new rare earth metal chloride complexes supported by a bridged-indenyl ancillary ligand, [C9H6SiMe2- （CH2）2SiMeEC9H6]Ln（u-Cl）2Li（TMEDA） [Ln=Y （1）, Lu （2）], were synthesized via salt metathesis reaction. Reaction of C9H7SiMeE（CH2）ESiMeEC9H7 with 2 equiv, of n-butyllithium in hexane at room temperature afforded [C9H6SiMe2- （CHE）2SiMeEC9H6]Li2 as white powder in 95% isolated yield. Further treatment of [C9H6SiMe2（CHE）2SiMeE- C9H6]Li2 with anhydrous LnCl3 in 1 ： 1 molar ratio in THF/TMEDA at room temperature provided the bridged-indenyl rare earth metal chlorides 1 and 2 in 86%--89% isolated yields. Both complexes were characterized by FT-IR spectroscopy, NMR spectroscopy, elemental analysis, and X-ray single crystal structure analysis. The central metals in both complexes are eight-coordinated by two indenyl ligands in η^5-fashion, and two chlorine atoms to adopt a distorted tetrahedral geometry.

Spectroscopy Study on Crystal Structure of Ce(NO_3)_3(phen)_2 and Interactions of Ce(NO_3)_3(phen)_2 with DNA

The absorption, fluorescence and Raman spectra of Ce(NO3)(3)(phen)(2) complex were assigned and the crystal structure of the complex was studied. Meanwhile the interactions between Cc (NO3)(3) (phen)(2) and DNA were studied by spectrum methods. As DNA was added, it is found that both the UV absorption bands of Ce(NO3)(3)(phen)(2) and the SERS bands of Ce(NO3)(3)(phen)(2) weaken evidently, while the fluorescence intensity of Ce(NO3)(3)(phen)(2) enhance dramatically. The complex compete against EB on the reaction with DNA. It is indicated by this spectrum methods that there are strong interactions between Ce(NO3)(3)(phen)(2) and DNA, and the bond mode is intercalation. The bond constant of the complex with DNA is determined to be 1.7 x 10(5).

Characterization, crystal structure and luminescence properties of a new europium(III) complex with macrocyclic ligand derived from 2,6-diformyl-4-methylphenol and diethylenetriamine

The title compound （13,27-dimethyl-3,6,9,17,20,23-hexaazatricyclo-[23.3.1.1^11,15]-triaconta-1 （29）,2,9,11,13,15（30）, 16,23,25,27- decaene-29,30-diol-N^3, N^6, N^9, O^29, O^30）-bis （nitrato-O,O＇）-europium （Ⅲ） nitrate hydrate （[EuL（NO3）2]（NO3）·H2O, L denotes the macrocyclic ligand） was prepared and characterized by elemental analysis, infrared spectra, and electrospray mass spectra. Its crystal and molecular structure was determined by X-ray diffraction. The crystal crystallized in the monoclinic system, space group C2/c with a=2.3757 （4） nm, b=1.4302（3） nm, c=1.9584（3） nm, β=91.654（5）°, M=818.60, V=6.651（2） nm^3, Z=8, D=1.635 g/cm, F（000）=3312, R=0.0542, wR=0.1045. The central ion Eu^3＋ was nine-coordinated in the coordinaton geometry of a distorted tricapped trigonal prism. The macrocycle was coordinated through two oxygen and three nitrogen atoms. Two nitrate are chelate in the opposite positions of the macrocycle, the third nitrate being ionic. At room temperature, excitation of the title complex gave rise to the characteristic emissions of the Eu^3＋ ion.

Crystal Structure and Luminescence Property of Lanthanide Complexes with 2-Fluorobenzoic Acid and 2,2′-Bipyridine

The two compounds of [Ln（2-FBA）3·2,2＇-bpy ]2（2-FBA = 2-fluorobenzoato, 2,2＇-bpy = 2,2＇-bipyridine, Ln = Eu（1 ）, Dy（2）） were synthesized and their structures were determined by X-ray diffraction method. Crystallized complexes 1 and 2 are isomorphous, monoelinie system with P21/n space group. The two complexes are binuclear molecule with an inversion center. The two lanthanide ions are linked by four bridged 2-FBA ligands and each lanthanide ion is further bonded to one chelated bidentate 2-FBA ligand and one 2,2＇-bipyridine molecule. The coordination number of metal ion is eight. The europium complex exhibits strong red fluorescence. ^5D0→^7Fj（j = 1 - 4） transition emission of Eu^3＋ ion was observed.

Crystal Structure and Properties of Europium m-Chlorobenzoate Complex with 1,10-Phenanthroline

A europium m-chlorobenzoate complex with 1,10-phenanthroline [Eu(m-ClBA)_3(phen)]_2 single crystal, where m-ClBA=m-chlorobenzoate and phen=1,10- phenanthroline,was prepared and structurally characterized by X-ray diffraction. It crystallizes in triclinic, space group P1- with a=1.10138(8)nm, b=(1.18606(9) nm,) c=1.32516(10) nm, α=112.5390(10)°, β=92.1700(10)°, γ=101.6220(10)°,(C_(66))H_(40)N_4O_(12)Cl_6Eu_2, M_r=1597.64, V=1.5533(2) nm^3, Z=1, D_c=1.708 g·cm^(-3), μ(Mo Kα)=2.325 mm^(-1), (F(000))= 788, the final R=0.0424 and wR=0.0899 for 6856 independent reflections with R_(int)=(0.0776.)The crystal consists of binuclear molecules of the title compound. Each Eu^(3+) ion is nine-coordinated to one 1,10-phenanthroline molecule, one bidentate carboxylate group and four bridging carboxylate groups. The carboxylate groups are bonded to the europium ion in three modes: the chelating bidentate, the bridging bidentate and bridging-chelating thridentate. Excitation and luminescence data observed at room temperature show that the title complex (emits) very intensive red fluorescence under ultraviolet light. The results of thermal analysis indicate that the complex [Eu(m-ClBA)_3(phen)]_2 is quite stable to heat.

Synthesis, Crystal Structure and Fluorescent Properties of a New One-Dimensional Polymer [Sm(sal)_4(phen)_2Na]_n

The title complex, [Sm(sal)_4(phen)_2Na]_n (Ⅰ), where Hsal=salicylic acid, phen=1, 10-phenanthroline, was synthesized by the reaction of samarium chloride with phen and Hsal in ethanol solution and its crystal structure was determined by X-ray diffraction. The crystal is monoclinic, space group C2/c with cell dimensions of a=2 84989 (7) nm, b=0 93347 (2) nm, c=2.27954 (5) nm, β=132.4010 (8)°, V=4.4781 (2) nm^3, Z=4, μ (Mo Kα)=13.97 cm^(-1), D_c=1.605 g·cm^(-3). The title complex is a compound, with centre of the Sm and Na atoms which are bridged by two carboxylate ligands. The structure of the complex demonstrates one-dimensional chain bridged by carboxyl groups. The fluorescence spectrum of the complex indicates that the second ligand phen shows enhancement effect on the fluorescence of the complex.

Synthesis,crystal structure and fluorescence of a new europium complex with 2-bromobenzoate and 2,2'-bipyridine

A new complex of {[Eu2(2-BrBA)6(2,2’-bpy)2]2·CH3CH2OH·H2O} (2-BrBA=2-bromobenzoate; 2,2’-bpy=2,2’-bipyridine) was prepared by solvent method and characterized with X-ray single-crystal diffraction, IR spectroscopy, UV spectroscopy, and fluorescence spectroscopy. The complex crystallized in triclinic crystal system, Pī space group, with a=1.17196(4) nm, b=2.36142(9) nm, c=2.59151(9) nm, α=113.266(2)°, β=101.100(2)°, and γ=94.400(2)°. Two independent dinuclear molecules were contained in the asymmetric unit. The two molecules were similar to each other. Each Eu(Ⅲ) ion was nine-coordinated with seven oxygen atoms from five 2-BrBA ligands and two nitrogen atoms from 2,2’-bpy molecule. The carboxylate groups acted as bidentate-chelating, bidentate-bridging and chelating-bridging coordination modes. The complex adopted a distorted monocapped square-antiprism coordination geometry. Five peaks at 579, 591, 613, 652, and 697 nm appeared in the fluorescence spectrum, corresponding to 5D0→7F0, 5D0→7F1, 5D0→7F2, 5D0→7F3, and 5D0→7F4 transition emissions of the Eu(Ⅲ) ion, respectively.

Crystal Structure and Luminescence Spectra of Novel Coordination Layer of {[Eu(m-BDC)(NO_3)(Phen)(H_2O)]_2·2CH_3CH_2OH}_n

The crystal structure of a novel Eu^(3+) coordination polymer, {[Eu(m-BDC)(NO_3)(Phen)(H_2O)]_2·2CH_3CH_2OH}_n (m-BDC=1,3-benzenedicarboxylate, Phen=1, 10-phenanthroline), was obtained and its high-resolution luminescence spectra at 77K were measured. The μ_2-carboxylate of m-BDC constructs the binuclear building block in which each Eu^(3+) ion is coordinated by four oxygen atoms of m-BDC anions, one oxygen atom from water molecule, two oxygen atoms of nitrate and two nitrogen atoms of Phen, respectively. The μ_1-carboxylate of m-BDC conjugates the binuclear units one-dimensional chain or a ribbon, while the hydrogen bonds between ribbons assemble the structure two-dimensional layer with a thickness equaling to the width of the ribbon. The luminescence spectra reveal that the two Eu^(3+) ion sites in the binuclear building blocks have slight environmental difference. The C_1 local symmetry of Eu^(3+) ion is concluded from both crystal structure measurement and luminescence spectra.

Synthesis and crystal structure of sodium praseodymium polyphosphate, NaPr(PO_3)_4

Reaction of Na2CO3, Pr6O11 and H3PO4 gave the sodium praseodymium polyphosphate NaPr（PO3）4.The title compound crystallized in the monoclinic P21/n space group with a=0.9965（4） nm, b=1.31437（4） nm, c=0.72271（3） nm, β=90.429（3）°, V=0.9465（4） nm3, Z=4, R=0.0493 and wR=0.1266 for 1855 independent reflections.The structure of NaPr（PO3）4 consisted of PrO8 polyhedra sharing oxygen atoms with phosphoric group PO4 to form a three-dimensional framework, delimiting intersecting tunnels in which the sodium ion was located.Each Na＋ ion was bonded to seven oxygen atoms.