Hydrothermal synthesis, crystal structure and luminescence of a europium complex with phenylmalonic acid and 1, 10-phenanthroline

A new complex Eu2（PA）6（phen）2 was prepared with hydrothermal reaction using EuCl3.6H2O, phenylmalonic acid （H2phma）, and 1, 10-phenanthroline （phen）, where PA was the decarboxylated product of HEphma, phenylacetate. The crystal structure of the title complex was determined with the X-ray diffraction. The title complex was a binuclear molecule with an inversion center. Each Eu^3＋ ion was nine-coordinated with two nitrogen atoms from one phen molecule and seven oxygen atoms from five PA ligands. The carboxylic groups were bonded to the Eu^3＋ ion in three modes, the chelating bidentate, the bridging bidentate, and the bridging-chelating tridentate. The complex emits intense red fluorescence under ultraviolet light. The luminescence peaks correspond to the characteristic emission 5D0→7FJ （J=0-4） transitions of the Eu^3＋ ion.     

Synthesis and crystal structure of a novel double 1：11 series arsenotungstate： [Cu^I（phen）2]5H6[Sm（AsW11O39）2]·6H2O

A novel double 1：11 series arsenotungstate, [Cu^I（phen）2]5H6[Sm（AsW11O39）2]·6H2O （phen=1, 10-phenanthroline） was synthesized by the hydrothermal method and characterized by elemental analysis, 1R spectra, and single-crystal X-ray diffraction. The title compound was monoclinic, space group P2 1/c, a=3.75710（2） nm, b=1.39776（8） nm, c=-3.33735（18） nm, β=96.967（10）°, V=17.3969（17） nm^3, Z=4. Single crystal X-ray structural analyses revealed that the dimeric polyanion, [SmAs2W22O78]^1-, consisted of one central Sm^3＋ ion and two tetradentate heteropoly ligands [ASW11O39]^7-. The Sm^3＋ ion and two tetradentate defective [AsW11O39]^7- anions were joined together by the sharing of four oxygen atoms from each heteropoly ligand. The bond valence sum （BVS） calculations of the title compound suggested that all four Cu atoms were in the ＋1 oxidation sate.     

Luminescent Properties of Green Phosphor Ca8Mg（SiO4 ）4 Cl2：EU^2＋ , DY^3＋ for LED Applications

The new phosphor calcium magnesium chlorosilicate, codoped with Eu^2＋ and Dy^3＋, was synthesized with the help of the high temperature solid state reaction in reducing atmosphere. The excitation and emission spectra were very similar to that of Ca8Mg（SiO4）4Cl2 ：Eu^2＋, and the Dy^3＋ concentration influenced the emission intensity of this phosphor. The intensity of Eu^2＋ and Dy^3＋ codoped CMSC was stronger than that of Eu^2＋ singly doped CMSC. The emission spectrum of the Dy^3＋ ion overlapped the absorption band of the Eu^2＋ ion, indicating that an energy transfer from Dy^3＋ to Eu^2＋ took place in CMSC：Eu^2＋, Dy^3＋ phosphor. The mechanism of the energy transfer from Dy^3＋ tO Eu^2＋, in this phosphor, might be resonant energy transfer.     

Multiple Energy Transfers in Rare Earth Complex-Doped SiO2 Spheres

Silica spheres doped with Eu （TTFA）3 and/or Sm（TTFA）3 were synthesized by using the modified Stober method. The transmission electron microscope image reveals that the hybrid spheres have smooth surfaces and an average diameter of about 210 nm. Fluorescence spectrometer was used to analyze the fluorescence properties of hybrid spheres. The results show that multiple energy transfer processes are simultaneously achieved in the same samples co-doped with Eu （TTFA）3 and Sm（TTFA）3, namely between the ligand and Eu^3＋ ion, the ligand and Sm^3＋ ion, and Sm^3＋ ion and Eu^3＋ ion. Energy transfer of Sm^3＋→Eu^3＋ in the hybrid spheres leads to fluorescence enhancement of Eu^3＋ emission by approximately an order of magnitude. The lifetimes of the hybrid spheres were also measured.     

Effects of Doping Trace Sm^3＋ and Gd^3＋ on Luminescent Character of Y2O2S：Eu^3＋

After trace Sm^3＋ ions and Gd^3＋ ions doping, the emission intensity of red phosphors Y2O2S： Eu^3 ＋ was enhanced and the voltage character （relation between emission intensity and excitation voltage） was improved while the other properties of physics and chemistry were not changed. The origins of enhancement and improvement are discussed. Probably the distortion and the defect of crystals are decreased by the substitution of Gd^3＋ for Y^3＋ instead of Eu^3＋ for Y^3＋ , and thus the Eu^3＋ crystal field is improved, and radiationless process and energy loss resulted from crystal defect are weakened, which leads to increased luminescence intensity and voltage character improvement. The overlapping fluorescent spectra of Y2O2S： Sm^3＋ emission and Y2O2S：Eu^3＋ excitation as well as Eu^3 ＋ excitation spectra transitions spectra lead to energy transfer from Sm^3 ＋ sensitization of Sm^3＋ ions fectively. containing Sm^3＋ excitation the possibility of resonance ions to Eu^3＋ ions, and the to Eu^3＋ ions is achieved effectively.     

Luminescence properties of YAl3（BO3）4 phosphors doped with Eu^3＋ ions

YAl3 （BO3）4： Eu^3＋ phosphors were prepared by the conventional solid state reaction. The phase structure and morphology were investigated by X-ray diffraction （XRD） and scanning electron microscope （SEM）. Doping YAl3（BO3）4： Eu^3＋ phosphors with concentration of Eu^3＋ ions of 0, 2, 5, 8 and 10 mol% were studied and their luminescent properties at room temperature were discussed. The excitation spectrum of Y0.95Eu0.05Al3（BO3）4 was composed of a broad band centered at about 252 nm and a group of lines in the longer wavelength region. In the emission spectra, the peak wavelength was about 614 nm under a 252 nm UV excitation. The optimal doping concentration of Eu^3＋ ions in YAl3（BO3）4： Eu^3＋ phosphors was 8 mol%.     

A new polyoxometalate based on mono-lacunary Dawson polyoxoanion： molecular structure of [{Nd（H2O）3（α2-P2W17O61）}2]^14-

A new polyoxometalate dimer based on lacunary Wells-Dawson anion and lanthanide cation, Na14[{Nd（H2O）3 （α2-PeWt7O61）2]·17H2O, was isolated as a sodium salt under ambient conditions and characterized by IR, TG, and X-ray single crystal structure analysis and electrochemistry. It belonged to the triclinic, space group Pi with a=1.26738 （15） nm, b=1.41464 （17） nm, c=2.3254 （4） nm, α=103.142 （2）°, β = 95.122 （2）°, γ=113.9690 （10）°, V=3.6317 （8）nm^3, Z=2, Dc=4.274 mg/m^3, and μ=27.695 mm^-1. The Nd^3＋ ion was substituted for a [W=O]^4＋ unit in the ＂cap＂ site of the tungsten-oxygen framework of the parent Wells-Dawson ion. The cyclic voltammograms of the title compound exhibited nearly chemically reversible one-step one-electron transfer process and two-step irreversible reduction processes. Thermogravimetric showed a one-step slow weight loss stage in the range of 25-850 ℃.     

VUV Spectroscopy of GdPO4： Eu^3＋ and GdBO3： Eu^3＋

The emission and the excitation spectra of GdPO4 ： Eu^3＋ and GdBO3： Eu^3 ＋ prepared by solid state reaction method were investigated using the synchrotron radiation source of SUPERLUMI station of HASYLAB. The energy transfer between Gd^3＋ and Eu^3＋ was discussed with the probability of quantum cutting process. In the excitation spectra monitoring the red emission from Eu^3＋ , the distinct lines corresponding to the intraconfigurational 4f-4f transitions from Gd^3＋ were observed for both samples, indicating an efficient energy transfer from host Gd^3＋ ions to the doped Eu^3＋ ions. The efficient energy transfer is necessary for the quantum cutting process based on the two-step energy transfer from Gd^3＋ to Eu^3＋ . However, the overlapping of the lines corresponding to Gd^3＋ ：^8S7/2→^6GJ and the broad excitation band （180 - 270 nm） due to Eu^3＋- O^2- charge transfer states （CTS） around 200 nm cause excitation energy on ^6GJ levels to dissipate into CTS by direct energy transfer, unfavorable to the cross relaxation energy transfer between Gd^3＋ and Eu^3＋, thus unfavorable to the quantum cutting process. With the help of the general rules governing the energy positions of Eu^3＋-O^2- ：CTS, the suggestions concerning searching suitable oxide hosts for Gd^3＋-Eu^3＋ quantum cutting were made.     

Synthesis and Properties of Eu Activated Strontium Molybdate Phosphor

In order to prepare fluorescent material for white Light Emitting Diodes （LEDs）, a new Eu^3＋ activated molybdate phosphor SrMoO4 was fabricated with solid-state method. X-ray diffraction （XRD） showed that the doping of trivalent europium ion reduced the lattice parameters. The excitation and emission spectra indicated that this phosphor could be excited effectively by the visible light, and then emitted red light with the peaks located at 616 and 624 nm. The influence of Eu^3＋ concentration on the luminescent properties of Eu^3＋ doped SrMoO4 was investigated and the 25% （mole fraction） was the appropriate molar concentration. The reaction time and temperature had obvious effect on the luminescent properties. The luminescent intensity reached the strongest when it was sintered at 800 ℃ for 3 h.     

Luminescent characteristics of Ba3Y2（BO3）4：Eu^3＋ phosphor for white LED

The Ba3Y2（BO3）4：Eu^3＋ phosphor was synthesized using a high temperature solid-state reaction method and the luminescent characteristics were investigated. The emission spectrum exhibited one strong red emission at 613 nm, corresponding to the electric dipole 5D0-TF2 transition of Eu^3＋, under 365 nm excitation. The excitation spectrum of 613 nm indicated that the Ba3Y2（BO3）n：Eu^3＋ phosphor was effectively excited by ultraviolet （UV） （254, 365 and 400 nm） and blue （470 nm） light. The effect of Eu^3＋ concentration on the 613 nm emission of the Ba3Y2（BO3）n：Eu^3＋ phosphor was measured. The results showed that the emission intensity increased with increasing Eu^3＋ concentration, and then decreased. The CIE color coordinates of Ba3Y2（BO3）4：Eu^3＋ phosphor were x=0.641 and y=0.359 at 15 mol.% Eu^3＋.     

Synthesis, Characterization, and Reactivity of Amine Bis（phenolato） Cyclopentadienyl Lanthanide Complexes

（C5H5）3Ln（THF）reacted with amine bis（phenol） LH2 [ L = Me2NCH2CH2N {CH2-（2-O-C6H2-But^1-3-Me- 5）}2 ] in a 1：1 molar ratio in THF to generate the amine bis（phenolato） cyclopentadienyl lanthanide complexes LLn（C5H5） （THF）·（THF）,（Ln = La （1）, n =0; Ln = Sm（2）, n = 1） in high yields. Complexes 1 and 2 were fully characterized by elemental analysis, NMR （for 1） and IR spectra, and X-ray structural determination. The crystal data of complex 1 are monoclinic, P21/c space goup, a= 1.1595（1） nm, b = 1.8588（2） nm, c = 1.6647（1） nm, β = 98.490（2）°, V =3.5486（5） nm^3, Z =4, Dc = 1.338 mg· m^3,μ = 1240 mm^-1, F（000）= 1488, R =0.0249, wR = 0.0568. The crystal data of complex 2 are monoclinic, P21/c sp ace goup, a = 0.9692 （1） nm, b = 1.4583 （2） nm, c = 2.8192 （3） nm, = 96.805 （2）°, V = 3.9584 （7） nm^3, Z=4, Dc =1.340 mg · ma, μ = 1.524 mm^-1, F（000）= 1668, R =0.0346, wR =0.0756. The attempts failed to synthesize the amine bis（phenolate） lanthanide alkoxides by the reactions of complexes 1 and 2 with alcohols. The preliminary results revealed that complex 1 can initiate ε-caprolactone polymerization.     

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 spectrscopy, and fluorescence spectroscopy. The complex crystallized in triclinic crystal system, PT space group, with a=1.17196(4) nm, b=-2.36142(9) nm, c=2.59151(9) nm, a=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 ni-trogen atoms from 2,2'-bpy molecule. The carboxylate groups acted as bidentate-chelating, bidentate-bridging and chelating-bridging coor-dination 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 emis-sions of the Eu(Ⅲ) ion, respectively.     

Synthesis, characterization and fluorescence of N,N'-BIS (6-metyl-2-pyridine-carboxylamide-N-oxide)-1,2-ethane and corresponding rare earth (Ⅲ) complexes

A new ligand, N,N-BIS (6-metyl-2-pyridinecarboxylamide-N-oxide)-1,2-ethane (L) and six lanthanide(III) complexes (RE=La, Sm, Eu, Tb, Gd, Yb) were synthesized and characterized in detail. The results indicated that the composition of the binary complexes was determined as [REL(H₂O)(NO₃)₂]NO₃·nH₂O (n=0–2), and the Eu³⁺ complex had bright red fluorescence in solid state. Three complexes of Eu³⁺, Tb³⁺, and Gd³⁺ with 6-methylpicolinic acid N-oxide (L') were also synthesized. The relative intensity of sensitized luminescence for Eu³⁺ increased in the following order: L>L'. The phosphorescence spectra of the Gd³⁺ complexes at 77 K were measured. The energies of excited triplet state for the ligands were 20704 cm⁻¹ (L) and 20408 cm⁻¹ (L'). The facts that the ligands sensitized Eu³⁺ strongly and the order of the emission intensity for Eu³⁺ complexes were explained by ΔE(T-⁵D). This meant that the triplet energy level of the ligand was the main factor to influence RE³⁺ luminescence.     

Hydrothermal synthesis and crystal structure study of two novel 3-D mellitates {Nd2[C6（COO）6] （H2O）6} and {Ho2[C6（COO）6]（H2O）6}

Two novel 3-D coordination compounds, Nd2[C6（COO）6]（H2O）6 （1）and Ho2[C6（COO）6]（H2O）6 （2）, were hydrothermaily synthesized from mellitic acid and neodymium perchlorate （or holmium perchlorate） in the alkaline aqueous solution and characterized with elemental analysis, TG, IR spectrum, and single crystal X-ray diffraction. The two compounds were isostructural and crystallized in the orthorhombic system, space group Pnnm, with a=1.3531 （4） nm, b=0.6687 （2） nm, c=1.0224（3） nm, V=0.92523（5） nm^3, Z=4, D=2.630 g/cm^3, F（000）=696.0, Goof=1.052. Final R indices [1 〉2∑（Ⅰ）]： R1=0.0195, wR2=0.0382 for 1; a=1.3411 （2） nm, b=0.6586（1） nm, c=1.0116（2） nm, V=0.8935（3） nm^3, Z=4, D=2.877 g/cm^3, F（000）=724.0, Goof=1.061. Final R indices [1 〉2∑（Ⅰ）]： R1=0.0200, wR2=0.0479 for 2. In the two compounds 1 and 2, the mellitic acid ligand, in which all the carboxylate groups were deprotonated, had only one kind of coordination mode to bridge metal ions to form four-connected three-dimensional diamondiod networks.     

Synthesis and Characterization of the First Dinuclear Europium （Ⅱ） Complex Supported by Carbon-Bridged Biphenolate Ligand

Amongpossiblealternativestothetraditionalan cillaryligandbis(cyclopentadienyl)setinrareearth metalchemistry,alkoxides(aryloxides)havereceived muchattentionandbecomeincreasinglypopularsince theyareeasilyavailable,tunableandevenpotentially recyclableancillarysetsformediatingthereactivityof theseelectropositivecations[1,2].Thechelatebiphenol andbinaphtholhavebeenfoundtobeabletoactasa dianionicligandintherareearthchemistry,whichhas theadvantagesofavoidingligandredistributionreac tions,andallowingth…     

Synthesis and Characterization of A Polynuclear Yttrium Trifluoroethoxide and Its Activity for Oligomerization of Phenyl Isocyanate

A polynuclear yttrium trifluoroethoxide was synthesized and its activity for the oligomerization of phenyl isocyanate was tested. Reaction of anhydrous YCl3 with CF3CH2ONa in a 1:3 molar ratio in THF at room temperature, after workup, gave complex 1 as colorless crystals. The composition of complex 1 is [Y(OCH2CF3)3]6ONa2(THF)12, which was identified by elemental analysis and 1H NMR. Further X-ray structure determination reveals that complex 1 is a polynuclear ion pair compound, [Y6(μ6-O)(OCH2CF3)18]2-[Na(THF)6] 2 (1). The crystal data of complex 1 are trigonal, P-3 space group, a=1.78440(14) nm, b=1.78440(14) nm, c=1.27395(12) nm, γ=120°, V=3.5129(5) nm3, Z=1, Dc=1.607 mg·m-3, μ=2.591 mm-1 (Mo Kα), F(000)=1710, R=0.067, wR=0.182. Preliminary results demonstrated that complex 1 is a highly effective catalyst for the oligomerization of phenyl isocyanate.     

Synthesis and luminescence properties of a novel red-emitting phosphor SrCaSiO_4：Eu~（3＋） for ultraviolet white light-emitting diodes

A novel red phosphor based on Eu3+-activated SrCaSiO4 was successfully synthesized by conventional solid state reaction method and the photoluminescence properties were investigated. X-ray diffraction (XRD) patterns indicated that SrCaSiO4:Eu3+ phosphors belong to orthorhombic crystal system (space group=Pmnb). The photoluminescence (PL) excitation spectrum showed broad-band absorption and the strongest excitation peak at 397 nm contributed to the 7F0→5L6 transition which matched well with the emission of a...     

Crystal structure and infrared spectrum of thallium holmium polyphosphate,TIHo（PO3）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 crystal structure of a 1D chainlike rare earth coordinated tungstogermenate： [（CH3）4N]1.50H3.50[Gd（GeW11O39）（H2O）2]·2.5H2O

A 1D 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 Gd3+ 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 GdⅢ cations.     

Vacuum ultraviolet excited photoluminescence properties of Gd2O2CO3：Eu^3＋ phosphor

The Gd2O2CO3：Eu^3＋ with type-Ⅱ structure phosphor was successfully synthesized via flux method at 400 ℃ and their photoluminescence properties in vacuum ultraviolet （VUV） region were examined. The broad and strong excitation bands in the range of 153-205 nm owing to the CO3^2- host absorption and charge transfer （CT） of Gd^3＋-O2^- were observed for Gd2O2CO3：Eu^3＋. Under 172 nm excitation, Gd2O2CO3：Eu^3＋ exhibited strong red emission with good color purity, indicating Eu^3＋ ions located at low symmetry sites and the chromaticity coordination of luminescence for Gd2O2CO3：Eu^3＋ was （x=0.652, y=0.345）. The photoluminescence quenching concentration of Eu^3＋ excited by 172 nm for Gd2O2CO3：Eu^3＋ was about 5%. Gd2O2CO3：Eu^3＋ would be a potential VUV-excited red phosphor applied in mercury-free fluorescent lamps.