Crystal structures and fluorescence properties of lanthanide complexes prepared with 2,2’-biphenyldicarboxylic acid and 2,2’：6’,2’’-terpyridine

Five lanthanide complexes of Ln₂(dpdc)₂(tpy)₂(NO₃)₂(H₂O)₂ [Ln=La (1), Ce (2), Pr (3), Sm (4), Gd (5), H₂dpdc=2,2’-biphenyldicarboxylic acid and tpy=2,2′:6′,2″-terpyridine] were prepared at room temperature and characterized by X-ray diffraction, FT-IR and thermo-gravimetric analysis. The results showed that complexes 1–5 were isostructural and consisted of dinuclear units [Ln₂(dpdc)₂(tpy)₂(NO₃)(H₂O)₂] bridged by two dpdc^2? ligands. The dinuclear units with strong intramolecular hydrogen bonds were assembled into 2D supramolecular layers by the weak π^…π staking interactions between pyridine rings of tpy. The TG analysis showed that the complexes 1–5 behaved higher thermal stability with no mass loss at < 320 °C. The lanthanide contraction effect and the solid state luminescence properties of complexes 1–5 were also investigated. The luminescence emission spectra of complexes 1–5 exhibited ligands emission bands and complex 3 and 4 had no typical emission in the visible region.     

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.     

Synthesis, spectroscopic characterization and thermal studies of some lanthanide(Ⅲ) nitrate complexes with a hydrazo derivative of 4-aminoantipyrine

A heterocyclic ligand synthesized by the coupling of diazotized 4-aminoantipyrine with acetylacetone reacted with lanthanide(III) nitrate to form complexes of the type [Ln(HAAP)₂(NO₃)₃] where, Ln=La(III), Ce(III), Pr(III), Nd(III), Sm(III), or Gd(III) and HAAP= 3-{[2-(N-1-phenyl-2,3-dimethylpyrazol-3-in-5-on-4-yl)]hydrazone}pent-2,3,4-trione. The ligand and metal complexes were characterized on the basis of elemental analysis, molar conductance, magnetic susceptibility measurements, UV-Visible, infrared, far infrared and proton NMR spectral data. The spectral data revealed that the ligand existed in the hydrazo form and coordinated to the metal ion without deprotonation in a neutral tridentate manner, through carbonyl oxygen of pyrazolone ring, hydrazo nitrogen and carbonyl oxygen of the acetylacetone moiety. The molar conductance values adequately supported their non-electrolytic nature. The ligand and the praseodymium(III) complex were subjected to X-ray diffraction studies. Thermal decomposition behavior of the lanthanum(III) complex was also examined.     

Synthesis, Characterization and Fluorescence of Terbium（Ⅲ） Complexes with Phenylglyoxylic Acid and 2,2-Dipyridine, 1,10-Phenanthroline, Triphenyl Phosphine Oxide

Three new complexes TbL3dipy （H2O）2, TbL3phen （H2O） 2 and TbL2 （TPPO） 2NO3 were synthesized （L = phenylglyoxylate ion, dipy = 2, 2-dipyridine, phen = 1,10-phenanthmline, TPPO = Triphenyl phosphine oxide）. Elemental analysis, conductivity, IR spectra, and ^1HNMR spectra studies were performed. IR spectra indicate that the carboxylate ion of phenylglyoxylate is coordinated to the Tb（Ⅲ） ion as an unidentate ligand. In ^1HNMR, the signals of different hydrogens in phenylglyoxylate ion shift upfield. The excitation and emission spectra of the three solid complexes were recorded at morn temperature, in which the optimum excitation wavelengths are, 361.0, 359.0 and 367.0 nm for these three complexes, respectively. Four emission bands due to the ^5D4-^7Fj（j = 6, 5, 4, 3） transitions were observed for TbL3dipy（H2O）2（489.0, 545.0, 584.0, 620.0 nm） and TbL3phen（H2O）2（490.0, 544.0, 583.0, 620.0 nm）. Under the same conditions, only one emission band due to the ^5D4-^7F5 transition was observed for the complex TbL2（TPPO）2NO3. The emission intensity of TbL3dipy（H2O）2 is the strongest among the three complexes.     

Effects of cerium precursors on surface properties of mesoporous CeMnO_x catalysts for toluene combustion

Mesoporous CeMnOx composite oxides catalysts were prepared by surfactant-assisted co-precipitation method and used for the catalytic oxidation of toluene.The effect of different cerium precursors[Ce(NO_3)_3 and(NH_4)_2 Ce(NO_3)_6] on catalyst structure,surface properties and toluene combustion activities of mesoporous CeMnO_x catalysts were investigated.The Ce(Ⅲ)MnO_x catalyst prepared from Ce(NO_3)_3 precursor shows higher catalytic activity,with a 90% conversion temperature of 240℃,which is better than the Ce(Ⅳ)MnO_x catalyst derived from(NH_4)_2 Ce(NO_3)_6] precursor.On the basis of characterizations,it reveals that abundant surface content of Mn~(4+),better redox behavior and larger concentration of surface active oxygen species are responsible for the excellent catalytic performance.     

Microwave assisted synthesis,spectroscopic, thermal,and antifungal studies of some lanthanide（Ⅲ） complexes with a heterocyclic bishydrazone

A bishydrazone formed by the condensation of isatinmonohydrazone and salicylaldehyde reacted with lanthanide（Ⅲ） chloride to form complexes of the type [Ln（HISA）2Cl3], where, Ln=La（Ⅲ）, Ce（Ⅲ）, Pr（Ⅲ）, Nd（Ⅲ）, Sm（Ⅲ）, Eu（Ⅲ）, or Gd（Ⅲ） and HISA= [（2-hydroxybenzaldehyde）-3-isatin]bishydrazone. Both reactions were carried out under microwave conditions. The ligand and the metal complexes were characterized on the basis of elemental analysis, molar conductance, magnetic susceptibility measurements, UV visible, infrared, far infrared, and proton NMR spectral data. The ligand acted as neutral tridentate, coordinating through the carbonyl oxygen, azomethine nitrogen, and phenolic oxygen without deprotonation. The ligand and lanthanum（Ⅲ） complex were subjected to X-ray diffraction studies. The X-ray diffraction pattern of ligand exhibited its crystalline nature and that of the lanthanum（Ⅲ） complex indicated its amorphous character. The thermal decomposition behaviour of the complex, [La（HISA）2Cl3], was examined in the temperature range of 40-800 ℃ using TG, DTG, and DTA. The ligand and the metal complexes were screened for their antifungal activities.     

Chemical equilibrium constants of rare earth nitrates and tri-n-butyl phosphate complex formation

Mixed rare earth nitrates (REi(NO3)3) in the aqueous solution was mixed with tri-n-butyl phosphate (TBP, (n-C4H9O)3PO) dissolved in kerosene for the formation of their corresponding complexes (REi(NO3)3·ni(n-C4H9O)3PO) at 303 K. The effects of initial concentrations of both TBP and mixed rare earth nitrates on the equilibrium constants of their complex formations were investigated. The complexes were formed almost immediately after mixing. The simultaneous formations reached their chemical equilibria within a few minutes by shaking the mixture at 200 r/min. The chemical equilibrium constants of the complex formations were independent of the initial TBP concentrations. However, they were decreased by reducing the concentration of REi(NO3)3. All equilibrium constants of the simultaneous complex formations were less than 0.7, while the average molar ratio of TBP to REi(NO3)3 of the complexes varied between 1.0 and 1.6. The chemical equilibrium constant for the formation of La(NO3)3·(n-C4H9O)3PO was 0.09, while that of Dy(NO3)3·(n-C4H9O)3PO was 0.68. The ascending sequence of chemical equilibrium constants for the simultaneous formations was La, Ce, Pr, Nd, Eu, Y, Sm, Gd, and Dy.     

Synthesis and crystal structures of La(III), Y(III) complexes of homoveratric acid with 1,10-phenanthroline

Two three-dimensional complexes [Ln(DMPA)₃phen]₂ (HDMPA=3,4-dimet hoxyphenylacetic acid, homoveratric acid; Ln=La, Y; phen=1,10-phenanthroline) were synthesized under hydrothermal conditions and characterized with IR and emission spectra. The crystal structures were determined with single crystal X-ray diffraction method. The two compounds were isostructural, and 3D supramolecule architectures were formed by hydrogen bonds and π–π stacking interactions. They strongly emitted upon excitation due to π^*→π transition of the ligands.     

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     

Study on photodegradation of Azo dye by polyoxometalates/polyvinyl alcohol

A series of photocatalysts, K11[Ln(PW11O39)2]/PVA (Ln=La, Ce, Pr, Nd, Sm) were prepared by K11[Ln(PW11O39)2] (Ln=La, Ce, Pr,Nd, Sm) containing five kinds of lanthanides and polyvinyl alcohol as the support. The catalysts obtained were characterized by Fourier trans-form infrared spectra, UV-vis spectra, powder X-ray diffraction, and scanning electron microscopy, indicating that the structure of K11[Ln(PW11O39)2] and polyvinyl alcohol remained intact, respectively. The photocatalysts exhibited efficient catalytic activity to degrade methyl orange, Congo Red, Ponceau 2R. The maximal degradation conversions of the three kinds of dyes were 99.58%, 47.61%, 72.42%, respectively.     

Research on anti-corrosion property of rare earth inhibitor for X70 steel

Three kinds of rare earth nitrates were adopted to sodium molybdate to get three kinds of LnN-M compounded inhibitors(La(NO3)3+Na2MoO4(LaN-M),Ce(NO3)3+Na2MoO4(CeN-M),Pr(NO3)3+Na2MoO4(PrN-M)).The combination of weight-loss method and the electrochemical test,was used to evaluate and analyze the corrosion inhibition efficiency of these LnN-M inhibitors to make the research on their corrosion inhibition performance,and the sequential order of their performance was found as follows:CeN-M> LaN-M>PrN-M,among which,the inhibition efficiency of CeN-M for the X70 steel could reach 98.21%.The synergism parameters were calculated by weight-loss method,these computational data indicated that the synergistic effect between rare earth nitrates and sodium molybdate was obvious and significant.Surface morphology,chemical composition and phase components of the precipitation films were tested for discussing the mechanism of LnN-M inhibitors.The outer electronic configuration of the lanthanide was found to have an important influence on the inhibition efficiency.The CeN-M inhibitor was discovered to have the best inhibition effect with the amorphous cerium oxides.The results of this research revealed that the precipitation films formed on the surface of the steel samples had a crucial influence on the inhibition efficiencies after adding LnN-M inhibitors.     

Study on catalytic combustion of benzene over cerium based catalyst supported on cordierite

A series of MnCeOx catalysts supported on cordierite honeycomb (Cord) were prepared by a combustion synthesis method using Mn(NO3)2 , Ce(NO3 )2·6H2O and citric acid. The effect of the molar ratio of Mn/Ce, calcination time, the amount of citric acid and the effect of water vapor on the catalytic properties for the complete oxidation of benzene were investigated. These catalysts were characterized by X-ray diffraction (XRD), H 2 temperature-programmed reduction (H2 -TPR), O2 temperature programmed desorption (O2 -TPD) and scanning electron microscopy (SEM) techniques. The results indicated that the MnCeOx /Cord catalyst with Mn/Ce molar ratio of 1:1, calcining for 7h and M n+ /(citric acid) molar ratio of 6 exhibited the highest catalytic activity. When the concentration of benzene was 1500 ppm and the gaseous hourly space velocity was 20000h -1 , the conversion of toluene was 99.1% at the reaction temperature of 300 oC.     

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.     

Substituent effects on novel lanthanide(III) hydrazides complexes

New lanthanide (Eu³⁺ and Gd³⁺) complexes were successfully synthesized and the effect of the p-phenyl substituent on the Eu³⁺ luminescent properties was evaluated. In this sense, benzhydrazide, p-toluic hydrazide, 4-hydroxybenzhydrazide and 4-aminobenzoic hydrazide were used as ligands and the complexes were obtained by mixing the lanthanide salts with hydrazides in ethanol at room temperature and keeping the reaction for 2 h under mechanical stirring. Crystal of Gd-amino was obtained and its structure was elucidated by single-crystal X-ray diffraction, revealing that Gd³⁺ centered in a distorted tricapped trigonal-prismatic molecular geometry. IR spectroscopy and the elucidated structure confirm hydrazides acting as bidentate ligands binding to Ln³⁺ ions through the oxygen of carbonyl group and the nitrogen of terminal amine, forming a five-membered ring. CHN analyses confirm the molecular formulas [Gd(amino)₄(H₂O)](NO₃)₃·(C₂H₅OH) and [Eu(toluic)₃(H₂O)₃](NO₃)₃. Lower T₁ state energies are observed for ligands p-substituted with higher electron donating capacity groups, such as p-NH₂ and p-OH. In contrast, higher lifetimes and quantum efficiencies are obtained for Eu³⁺ complexes with ligands p-H and p-CH₃ substituted, which are not deactivator groups.     

Insertion Reactions of PhEtCCO and PhNCO into Ln-S （Ln = Er, Y, Yb） Bond of [Cp2Ln（μ-SEt） ]2

The reactivity of lanthanocene thiolates [Cp2Ln（μ-SEt）]2（Ln = Er, Y, Yb） with PhEtCCO and with PhNCO was examined. Treatment of [ Cp2Ln（μ-SEt）]2 with PhEtCCO gives the α-thiolate-substituted enolate complexes [ Cp2Ln （μ-η^1 ：η^3-OC（SEt）CPhEt）]2（Ln = Yb, Y）, while [Cp2Ln（μ-SEt）]2 react with PhNCO to give the lanthanocene amido derivatives [Cp2Ln（OC（SEt）NPh ）]2（Ln = Er, Yb）. In both cases, the insertion reaction is independent of the stoichiometric ratio and the nature of lanthanides, demonstrating that lanthanocene thiolates are high reactive toward PhEtCCO and PhNCO under the conditions involved. All complexes are characterized by elemental analysis and spectroscopic properties, of which the structures of ytterbium enolate and erbium amido are also determined by X-ray single crystal diffraction analysis, indicating that both of them are centrosymmetric binuclear structures.     

Synthesis and characterization of aminophenolate-ligated rare-earth metal amide complexes and their catalytic activity for lactides polymerization

Amine elimination of Ln[N(SiMe_3)_2]_3(μ-Cl)Li(THF)_3 with aminophenol H[ON] {H[ON]=2-(CH_2 NC_5 H_(10))-4,6-~tBu_2-C_6 H_3OH} in 1:2 molar ratio in THF gave the monometallic rare-earth metal amide complexes[ON]_2 LnN(SiMe_3)_2(Ln=Yb(1),Y(2),Gd(3),Sm(4),Nd(5)) in 57%-73% isolated yields.All these complexes were characterized by elemental analysis.The molecular structures of complexes 1-4 were determined by single crystal X-ray diffraction.These complexes are highly active for L-Iactide polymerization to give high molecular weight polymers with unimodal molecular weight distributions.In addition,these complexes can also initiate rac-lactide polymerization with high activity to afford heterotactic-rich polylactides.     

A novel material for passive NOx adsorber:Ce-based BEA zeolite

Passive NO_x adsorbers(PNAs) were proposed to address the NO_x emissions during the cold start phase.Here we show a novel Ce-based BEA zeolite,as a noble-metal-free passive NO_x adsorber.The NO_x adsorption capacity of Ce/BEA reaches 36 μmol/g in the feed gas close to realistic exhaust conditions,and the NO_x desorption temperature,which is around 290℃,is ideal for diesel exhaust after-treatment systems.Ce/BEA also behaves notable stability of hi...     

Dissociation of outer membrane for Escherichia coli cell caused by cerium nitrate

The biological effect of cerium nitrate on the outer membrane(OM) of Escherichia coli(E.coli) cell was studied,and the antim-icrobial mechanism of rare earth elements was explored.The antimicrobial effect of cerium nitrate on E.coli cell was valued by plate count method,and the morphology change of E.coli cell was observed with scanning electron microscopy(SEM) and transmission electron microscopy(TEM).The results showed that the E.coli cell suspension was flocculated when the concentration of Ce(NO3)3?6H2O...     

Promotional effects of cerium doping and NOx on the catalytic soot combustion over MnMgAIO hydrotalcite-based mixed oxides

A series of MnMgA10 samples with different amounts of Ce doping were facilely prepared using coprecipitation method and their catalytic soot combustion activity was evaluated by temperature programmed oxidation reaction （TPO）. The methods of X-ray diffraction （XRD）, Brumauer-Emmett-Teller （BET）, H2-TPR, NO-TPO and in situ 1R were used to characterize the physio- chemical properties of these samples. Dopant Ce improved the soot combustion performance of MnMgA10 catalyst due to the en- hanced redox ability. Introduction of NOx led to the further increase of catalytic soot oxidation activity on these samples. Over Ce-containing samples, the catalytic activity was slightly decreased as the amount of dopant Ce increased in 02. Diftbrently, in NO＋O2, a certain amount of dopant Ce was much more favorable and excess amount of Ce resulted in a sharp drop of the catalytic soot combustion activity. Both NO： and nitrates were found to have great contributions to the effects of NOx on the soot combustion activity of Ce-doped catalysts. More NO2 was generated as dopant Ce increased. When appropriate amount of Ce was introduced, the as-formed NO2 was stored as bridging bidentate nitrate on Mn-Ce site, which was confirmed to have higher reactivity with soot than nitrite or monodentate nitrate on Mn and/or Ce sites. Overall, Mno.sMg2.sCeo.lAlo.90 was considered as the most potential catalyst for soot combustion.     

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.