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 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…     

Measurements of Enthalpy Change of Reaction of Formation, Molar Heat Capacity and Constant-Volume Combustion Energy of Solid Complex Yb（Et2dtc）3（phen）

A ternary solid complex Yb(Et2dtc)3(phen) was obtained from the reaction of hydrous ytterbium chloride with sodium diethyldithiocarbamate (NaEt2dtc), and 1, 10-phenanthroline (o-phen·H2O) in absolute ethanol.The bonding characteristics of the complex were characterized by IR.The result shows Yb3 bands with two sulfur atoms in the Na(Et2dtc)3 and two nitrogen atoms in the o-phen.The enthalpy change of liquid-phase reaction of formation of the complex ΔrHθm (l), was determined as being (-24.838±0.114) kJ·mol-1 at 298.15 K, by an RD-496 Ⅲ type heat conduction microcalormeter.The enthalpy change of the solid-phase reaction of formation of the complex ΔrHθm (s), was calculated as being (108.015±0.479) kJ·mol-1 on the basis of an appropriate thermochemistry cycle.The thermodynamics of liquid-phase reaction of formation of the complex was investigated by changing the temperature during the liquid-phase reaction.Fundamental parameters, the activation enthalpy, ΔHθ≠, the activation entropy, ΔSθ≠, the activation free energy, ΔGθ≠, the apparent reaction rate constant k, the apparent activation energy E, the pre-exponential constant A, and the reaction order n, were obtained by a combination of the reaction thermodynamic and kinetic equations with the data from the thermokinetic experiments.At the same time, the molar heat capacity of the complex cm, p, was determined to be (86.34±1.74) J·mol-1·K-1 by the same microcalormeter.The constant-volume combustion energy of the complex, ΔcU, was determined to be (-17954.08±8.11) kJ·mol-1 by an RBC-Ⅱ type rotating-bomb calorimeter at 298.15 K.Its standard enthalpy of combustion, ΔcHθm, and standard enthalpy of formation, ΔfHθm, were calculated to be (-17973.29±8.11) kJ·mol-1 and (-770.36±9.02) kJ·mol-1, 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.     

Thermochemical Study on Coordination Complex of Samarium with Salicylic Acid and 8-Hydroxyquinoline

It is knownthat rare earthions ,8-hydroxyquino-line and salicylic acid are antibacterial[1 ～5].Synthesisand characterization of the rare earth complexes withsalicylic acid were reported by Sun[6].Synthesis andcharacterization of the rare earth complexes …     

Thermochemical Study on Ternary Solid Complex of La(Gly)2 (Ala)3 Cl3 ·2H2O (s)

The complex of lanthanum chloride with Glycine and Alanine, La(Gly)₂(Ala)₃Cl₃ · 2H₂O, was synthesized and characterized by IR, elementary analysis, thermogravimetric analysis, and chemical analysis. The dissolution enthalpies of LaCl₃ · 7H₂O(s), 2Gly(s) + 3Ala(s) and La(Gly)₂(Ala)₃Cl₃ · 2H₂O(s) were determined in 2 mol · L⁻¹ HCl by a solution-reaction isoperibol calorimeter. By designing a thermochemical cycle in terms of Hess' Law and through calculation, the reaction enthalpy of lanthanum chloride seven-hydrate with Glycine and Alanine was obtained: Δ_rH^θ_m(298.15 K) = (29.652 ± 0.504) kJ · mol⁻¹, and the standard enthalpy of formation of La(Gly)₂(Ala)₃Cl₃ · 2H₂O(s) Δ_fH^θ_m[La(Gly)₂ (Ala)₃Cl₃ · 2H₂O, s, 298.15 K] = −4467.6 ± 8.3 kJ · mol⁻¹.     

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, 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.     

Fluorescence and Judd-Ofelt analysis of rare earth complexes with maleic anhydride and acrylic acid

Two kinds of Eu-complexes, Eu(TTA)2(Phen)(AA) and Eu(TTA)2(Phen)(MA) (HTTA=2-Thenoyltrifluoroacetone, Phen=1,10- phenanthroline, AA=acrylic acid, MA=Maleic anhydride), which combined the excellent fluorescence properties of Eu(TTA)2(Phen)(H2O) and the reactivity of acrylic acid and maleic anhydride with radicals, were synthesized. The two complexes were characterized by elemental analysis, infrared (IR) spectra, and X-ray photoelectron spectroscopy (XPS). Based on the data shown from the fluorescent spectra of the Eu-MA and Eu-AA complexes, the ?λ (λ=2 and 4) experimental intensity parameters were calculated. The results demonstrated that the ?2 intensity parameters for the two complexes were smaller than those for the Eu(TTA)2(Phen)(H2O) complex, indicating that a less symmetri- cal chemical environment existed in the complexes. It implied that the radiative efficiency of the 5D0 of these two complexes could be en- hanced by ligand of MA and AA, respectively. The luminescent lifetime of the Eu-AA (τ=7.26×10–4 s) or Eu-MA complex (τ=8.12×10–4 s) was higher than that of the Eu(TTA)2(Phen)(H2O) complex, which was attributed to the substitution of the water molecule (H2O) in Eu(TTA)2(Phen)(H2O) by the MA or AA ligand.     

Characterization and alkaline decomposition–cyanidation kinetics of industrial ammonium jarosite in NaOH media

A complete characterization was carried out on a jarositic residue from the zinc industry. This residue consists of ammonium jarosite, with some contents of H₃O⁺, Ag⁺, Pb²⁺, Na⁺ and K⁺ in the alkaline “sites” and, Cu²⁺ and Zn²⁺ as a partial substitution of iron. The formula is: [Ag_0.001Na_0.07K_0.02Pb_0.007(NH₄)_0.59(H₃O)_0.31]Fe₃(SO₄)₂(OH)₆. Some contents of franklinite (ZnO^·Fe₂O₃), gunninguite (ZnSO₄·H₂O) and quartz were also detected. The jarosite is interconnected rhombohedral crystals of 1–2 μm, with a size distribution of particles of 2–100 μm, which could be described by the Rosin–Rammler model.The alkaline decomposition curves exhibit an induction period followed by a progressive conversion period; the experimental data are consistent with the spherical particle with shrinking core model for chemical control. The alkaline decomposition of the ammonium jarosite can be shown by the following stoichiometric formula:NH₄Fe₃(SO₄)₂(OH)_6(s)+3OH_(aq)⁻→(NH)_4(aq)⁺+3Fe(OH)_3(s)+2SO_4(aq)²⁻.The decomposition (NaOH) presents an order of reaction of 1.1 with respect to the [OH⁻] and an activation energy of 77 kJ mol⁻¹. In NaOH/CN⁻ media, the process is of 0.8 order with respect to the OH⁻ and 0.15 with respect to the CN⁻. The activation energy was 46 kJ mol⁻¹. Products obtained are amorphous. Franklinite was not affected during the decomposition process. The presence of this phase is indicative that the franklinite acted like a nucleus during the ammonium jarosite precipitation.     

Chemical conversions of osmium (VI) sulfite complexes in ammonia–sulfate solutions

It has been found that osmium (VI) sulfite complexes having composition [OsO₂(SO₃)₂(H₂O)₂]²⁻ in ammonia and sulfuric acid solutions enter into reaction of intrasphere substitution resulting in the formation of new complexes of osmium (VI). The rate of their formation depends on the concentration of constituents in the system and the temperature of solutions. Water-soluble ammonia–sulfite complexes of osmium (VI) (final form is [OsO₂(SO₃)₂(NH₃)₂]²⁻) are formed in ammonia-sulfate solutions. These complexes are converted into sulfate derivatives—water-soluble ([OsO₂(SO₃)(SO₄)(NH₃)₂]²⁻) and insoluble ([OsO₂(SO₄)₂(NH₃)₂]²⁻) in solutions containing (NH₄)₂SO₄ and H₂SO₄.     

Synthesis of pyrrolidinyl-ethylene fluorenyl rare-earth metal complexes and catalysis for 2-vinylpyridine polymerization

The metathesis reaction between pyrrolidinyl-ethylene fluorenyl lithium salts with in situ prepared cationic rare-earth metal dialkyl species [Ln(CH₂SiMe₃)₂(THF)_x][BPh₄] afford efficiently the corresponding constrained-geometry complexes L¹Ln(CH₂SiMe₃)₂(L¹=FluCH₂CH₂NC₄H₈,Ln=Y(1a),Lu(1b),Sc(1c)) and L² Ln(CH₂SiMe₃     

Structure regulation for ultra-high luminescence quantum yield lanthanide complex and simultaneous detection of cancer marker and ferrous ion

The exploitation of a highly selective and sensitive probe to detect both cancer marker and metal ion is of great importance.In this work,the "one stone two bird" agent of 1,10-phenanthroline(phen) is designed to disrupt the polymeric lanthanide MOFs(LnMOFs,[Ln(CHO_2)_3]n,Ln=Tb,la;Eu,1 b,CHO2=formic acid) {[Ln(CHO_2)_4·(C_2 H_8 N)]_n,Ln=Y,2 a;Gd,2 b;Dy,2 c,C_2 H_8 N=dimethylamine}) into a soluble mononuclear species [Ln(phen)2(NO_3)_3,Ln=Tb,3 a;Eu,3 b] as well as to provide an antenna for efficient photons absorption,resulting in an ultra-high luminescence quantum yield(QY,90%) europium complex.The luminescence QY is among the highest record of monomeric(zero-dimensional) lanthanide complexes.Furthermore,mononuclear Tb3+complex(3 a) functions as a multiplex sensor towards both Fe2+and cancer marker of 5-hydroxyindole-3-acetic acid(5-HIAA).Importantly,the limit of detection(LOD)for sensing 5-HIAA is an ultra-sensitive value of 1 × 10 s mol/L,which is even lower than that necessary for the early diagnosis of carcinoid tumors.More interestingly,sensing results in simulated urine reveals that 3 a has potential application for early diagnosis in the clinic.     

Organolanthanide Compounds Containing Methanesulfonate and Pyrazinamide Ligand in Styrene Polymerization

The synthesis of organolanthanide compounds identified as LnCp*(MS)2PzA, Ln=Sm, Tb, Yb (MS=methanesulfonate, Cp*=pentamethylcyclopentadienyl, and PzA=pyrazinamide), by the reaction of coordination compounds Ln(MS)3(PzA)4 with NaCp in THF was reported. The complexes were formulated according to elemental analyses, complexometric titration with EDTA (%Ln), and 1H NMR. IR spectroscopy revealed that PzA coordinates with lanthanide(Ⅲ) ions and methanesulfonate coordinates via oxygen atoms in a non-equivalent manner. In preliminary catalytic studies, these compounds were active in styrene polymerization that used MAO as a cocatalyst with an activity of 12.3 kg PS mol Sm-1h-1. Differential scanning calorimetry (DSC) of polystyrene showed that the polymer was mainly atactic.     

Preparation and Electrorheological Property of Y4O（OH）9（NO3）-NH4NO3 Materials

The new electrorheological (ER) material, a particle material composed of Y4O(OH)9(NO3) and NH4NO3, was obtained.They display better ER performance.The shear stress of the suspension of Y4O(OH)9(NO3)(NH4NO3)2.8 material in dimethyl silicone oil reaches 1469 Pa at an electric field strength (E) of 4.2 kV·mm-1 and the shear rate (γ) of 150 s-1.The relative shear stress, τE/τ0 (τE and τ0 are the shear stresses at E=4.2 and 0 kV·mm-1, respectively), is up to 29, which is 19 times that of pure Y2O3 material.The dielectric and conductive property of the materials play important roles in the modification of the ER effect of the particle materials.The researches on these new ER materials are very useful for obtaining a better understanding on the mechanism of the ER effect and finding an ideal ER material.     

Application of three Ln(Ⅲ)-coordination polymers in fields of luminescence,antibacteria and detection of Fe3+ and 4-nitrophenol

Three lanthanide-based coordination polymers(Ln-CPs) with layered structure,{[La₂(L)₃(DMF)(H₂O)₃]·H₂O}_n(1),{[Eu₂(L)₃(DMF)₂(H₂O)]·(H₂O)}_n(2){Tb₂(L)₃(DMF)₂(H₂O)]·H₂O}n(3) were successfully synthesized from H₂L(N,N’-bis(4-carbozylbenzyl)aniline).Remarkably,compound 3 has extremely high sensitivity to 4-n...     

Paramagnetic Anisotropy of CdGd2（WO4） 4-δ Single Crystal

CdGd2 （WO4）4 -δ single crystal was grown using the Czochralski＇s method. The crystal structure was tetragonal seheelite with lattice parameters a = b = 0.5203 nm and c = 1. 1359 nm. There were vacancies of （WO4）^2- , therefore, there were some Gd^2＋ ions. Langevin paramagnetism and anisotropy were observed from the δ-T curves at room temperature. The susceptibility X//was 3.5018×10^-3, and X⊥ was 3.4403× 10^-2. The anisotropy was also observed in the electron spin resonance （ESR） experiments. The anisotropic Land6 factors were g//= 2. 1333 and g~ = 2. 8411. The direction of easy magnetization was in the α-b plane. Anisotropic paramagnetic Curie constants C//and C⊥ were not only related to macroscopic a that was observed through the experiment, but were also related to J⊥ and J//, which were the microscopic quantum numbers of the Gd^2＋ and Gd^3｜ ions. Based on the detailed analyses, the proportion of 36.8% of Gd^3＋ ions to 63.2% of Gd^2＋ ions in the Gd ions of the CdGd2（WO4）4-δ crystal was calculated, and δ was 0.638 in the single crystal.     

Hydroxyl-and-carboxyl ligand concatenating multi-lanthanide substituted tellurotungstates and electrochemical detection of noradrenaline

Developing and exploring organic–inorganic hybrid multi-lanthanide (Ln) implanted heteropolyoxometalates (HPOMs) has bloomed into an emerging research field. In this article, two neoteric d-gluconic acids (H₆GA) concatenating multi-Ln^III implanted heteropolytungstates K₁₄H₁₀[Ln₄(H₂O)₄W₆(H₂GA)₄O₁₂(B-α-TeW₉O₃₃)₄]·60H₂O (Ln = La³⁺ (1), Pr³⁺ (2)) were obtained in acidic aqueous system. Attractively, in the polyanion structure of 1 and 2, six W^VI and four Ln^III centers are connected by four flexible H₂GA^4? ligands via carboxyl and hydroxyl groups, resulting in the heterometallic [Ln₄(H₂O)₄W₆(H₂GA)₄O₁₂]⁸⁺ cluster and then the heterometallic cluster is surrounded by four [B-α-TeW₉O₃₃]^8– segments. Electrochemical measurements for the 1@CFMCN/GCE sensor (CFMCN = carboxyl-functionalized multiwalled carbon nanotube; GCE = glass carbon electrode) demonstrate that 1@CFMCN/GCE shows benign recognition response to detecting noradrenaline (NDA). This research expands the structural diversity of Ln-implanted HPOMs and presents an electrochemical platform of recognizing NDA in the field of biosensors.     

Effect of Gallium Addition on Magnetic Properties of Nd2Fe14B-Based/ α-Fe Nanocomposite Magnets

The influence of Ga addition on the crystallization behavior and the magnetic properties of nanocomposite Nd2Fe14B-based/α-Fe magnets was investigated. It was found that the addition of 0.2% did not change the crystallization temperature of amorphous alloy, but the magnetic properties were improved significantly because of the strong exchange coupling interaction between the hard and soft magnetic phases. The optimum magnetic properties with iHc = 600. 3 kA· m^-1, B r = 0.75 T, and （BH）max = 88.03 kJ· m^-3 were obtained in bonded Nd9.5（FeCoZr）83.8 Ga0.3 B6.5 magnet with 15 m·s^- 1 wheel speed and 670 ℃ annealing treatment. The apparent improvement of magnetic properties originates from the grain refinement calculated using the Scherrer formula from corresponding XRD patterns and the excellent rectangularity of the demagnetization curve.     

Investigation on pumping oxygen characteristics of （Bi2O3）0.73（Y2O3）0.27 solid electrolyte

（Bi2O3）0.73（Y2O3）0.27 fine powders prepared by wet chemical precipitation method were cold isostatically pressed to form solid electrolyte tubes, and sintered at 900 ℃ for 10 h in the air. Their pumping oxygen characteristics in non-dehydrated Ar gas were investigated, where a ZrO2 （Y2O3 stabilized） oxygen sensor was used to measure the oxygen partial pressure Po2. The results showed that the Po2 value reached magnitudes of 1×10^-2-1×10^-10 Pa at the applied pumping oxygen voltage of 0.5 V, 1×10^-37-1×10^-27 Pa at 1.0 V and 1×10^-53-1×10^47 Pa at 2.0 V within the temperature range from 550 to 650 ℃. Moreover, no cracks were found in the tested solid electrolyte tubes. Thus, the Bi2O3-Y2O3 system might be used in solid electrolyte oxygen pump for purifying gases.