Synthesis, characterization and properties of some rare earth complexes with 2,6-pyridine dicarboxylic acid and α-Picolinic acid

Five novel ternary complexes were synthesized by the rare earth with 2,6-pyridine dicarboxylic acid andα-picolinic acid.These complexes were characterized by elemental analysis,molar conductivity,FT-IR,UV-Vis,Raman,TG-DTA and XRD.The general formula of the complexes was[RE(DPA)(L α )(H2O)]·2H2O(RE=Pr 3+ ,Nd 3+ ,Sm 3+ ,Eu,Er 3+ ;DPA=2,6-pyridine dicarboxylic acid;L α =α-picolinic acid). The investigation of fluorescence properties of the Eu-complex showed that the Eu(III)ion could be sensitized efficiently by the ligand to some extent.The antibacterial activity test indicated that all the five complexes exhibited antibacterial ability against Escherichia coli and Staphylococcus aureus with broad antimicrobial spectrums.     

Synthesis and Characterization of Rare Earth Complexes of Ferrocenylcarbonylhydrazine

Ｔｈｅｍｅｔａｌｃｏｍｐｌｅｘｅｓｏｆｈｙｄｒａｚｉｄｅｓｈａｖｅａｔｔｒａｃｔｅｄｃｏｎｓｉｄｅｒａｂｌｅｉｎｔｅｒｅｓｔｏｗｉｎｇｔｏｔｈｅｉｒａｎｔｉｆｕｎｇａｌａｎｄａｎｔｉｂａｃｔｅｒｉａｌａｃｔｉｖｉｔｉｅｓ[1 ,2 ] .Ｔｈｅｙｃａｎａｌｓｏｂｅｕｓｅｄａｓａｎａｌｙｔｉｃａｌｒｅａｇｅｎｔｓ[3 ]ａｎｄｅｘｔｒａｃｔｉｎｇａｇｅｎｔｓｆｏｒｍｅｔａｌｓａｌｔｓ[4 ] .Ｍａｎｙｃｏｍｐｌｅｘｅｓｏｆｈｙｄｒａｚｉｄｅｓｈａｖｅｂｅｅｎｓｙｎｔｈｅｓｉｚｅｄａｎｄｃｈａｒａｃｔｅｒｉｚｅｄ[5]…     

Synthesis, Catalysis of Rare Earth Complexes with Aliphatic Noncyclic Polyether-Amino Acid Schiff Base

Coordination chemistry of rare earth with Schiffbase has developed rapidly in the last fewyears ,butthe majority of the complexes studied are derivedfromaromatic Schiff base .So far less papers of rare earthcomplex with aliphatic Schiff base have been rep…     

Luminescence Properties of Sm^3＋ doped Bi2ZnB2O7

The phosphors of （Bi1- x Smx ） 2ZnB2O7 （ x = 0. 01, 0. 03, 0. 05, 0. 07, and 0. 09） were synthesized by conventional solid state reaction. The purity of all samples was checked by X-ray powder diffraction （XRD）. XRD analysis shows that all these compounds are of a single phase of Bi2ZnB2O7, indicating that the Bi^3＋ in Bi2ZnB2O7 can be partly replaced by the Sm^3＋ without the change of crystal structure. The excitation and emission spectra at room temperature show the typical 4f-4f transitions of Sm^3＋ . The dominant excitation line is around 404 nm due to ^6H5/2→^4K11/2 and the emission spectrum consists of a series of lines at 563, 599, 646, and 704 nm due to ^4G5/2→^6H5/2, ^6H7/2, ^6H9/2, and ^6H11/2, respectively. The optimal concentration of Sm^3＋ in Bi2ZnB2O7 is about 3mol% （relative to lmol Bi^3＋ ） and the critical distance Rc was calculated as 2.1 nm. The temperature dependence of the emission intensity of Bi1.94Sm0.06ZnB2O7 was examined in the temperature range between 100 and 450 K. The quenching temperature where the intensity has dropped to half of the initial intensity is 280 K. The lifetime for Sm^3＋ in Bi1.94Sm0.06ZnB2O7 is fitted as a value of 0.29 and 1.03 ms.     

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.     

Synthesis and crystal structure of novel samarium coordination polymer derived from sulfonic acid ligand

The self-assembly of HL(L=[5-(ethoxycarbonyl)-4-phenyl-3,4-dihydropyrimidin-2(1H)-one-6-yl]methanesulfonate) with Sm(ClO4)3·6H2O yielded a 2D coordination polymer {[SmL3(H2O)2]·4H2O}n(1).Its crystallographic data indicated that it belonged to a triclinic system,space group P-1,a=1.42233(8),b=1.47155(8),c=1.53868(9) nm,α=8.62710(10),β=6.35250(10),γ=71.5790(10)°,V=2.7241(3) nm3,Z=2,R1=0.0693,wR2=0.1054.X-ray analysis revealed that the local coordination environment around Sm(III) was a slightly distorted dodecahedron in which Sm center was eight-coordinate geometry with eight oxygen atoms from three sulfonic groups,three carbonyl groups and two aqua ligands.Each L-acted as a bidentate spacer to link two Sm centers,resulted in the formation of a 2D hexagonally grid network.The discrete 2D planes in 1 were assembled into a 3D supramolecular network via strong hydrogen bonds among noncoordinated aqua O atoms,coordinated aqua O atoms,and noncoordinated O atoms of sulfonic groups and carbonyl groups.Furthermore,this metal-organic polymer exhibited strong photoluminescence maximized at 379 nm upon 274 nm excitation in the solid state at room temperature.     

Synthesis and photoluminescent properties of doped ternary Eu_(1-x)Ln_x(NPPD)_3·DPQ complexes

Rare earth (RE) ternary complexes of Eu0.5Ln0.5(NPPD)3·(DPQ) (HNPPD=1-(naphthalen-2-yl)-3-phenylpropane-1,3-dione; DPQ= dipyridobenzoquinone) and Eu1-xLax(NPPD)3·(DPQ) (Ln3+=La3+, Gd3+, Sm3+, Pr3+; x=0.0, 0.1, 0.3, 0.5, 0.7, 0.9) were synthesized by the reaction of RECl3·6H2O with HNPPD and DPQ in stoichiometry. The complexes were characterized with IR, elemental analysis, TGA-DSC and wide-angle X-ray diffraction. The UV-Vis absorption spectra and fluorescence properties of the complexes were also investigated. The experimental results showed that the luminescence efficiency of Eu3+ complexes was enhanced by doping some other lanthanide ions. Eu0.7La0.3(NPPD)3·(DPQ) showed the highest luminescence efficiency.     

Synthesis, structures,thermal and magnetic properties of a series of lanthanide [Ln=Sm, Gd, Er, Yb] complexes with 4-quinolineacarboxylate

A series of lanthanide binuclear complexes, [Ln2(L)6(H2O)4]·2H2O (Ln=Sm(III), Gd(III), Er(III), Yb(III), HL=4-quinolineacarboxylic acid, were synthesized by reactions of corresponding rare earth salts with 4-quinolineacarboxylic acid at room temperature and were characterized by elemental analysis, IR spectroscopy, and single-crystal X-ray diffraction. X-ray diffraction analyses showed that they exhibited the same binuclear architecture and crystallized in monoclinic system and P21/c space group. In four complexes, each metal center adopted nine-coordinated mode coordinated by nine O atoms from two H2O molecules and three carboxyls of three ligands, and HL showed three different coordination modes. The variable-temperature magnetic susceptibility showed that complex [Gd2(L)6(H2O)4]·2H2O performed very weak antiferromagnetic property at low temperature and exchange was almost paramagnetic at high temperature. Complexes [Er2(L)6(H2O)4]·2H2O and [Yb2(L)6(H2O)4]·2H2O performed dominating antiferromagnetic coupling.     

Synthesis and antitumor activities of rare earth substituted phosphotungstates containing 5-fluorouracil

Two novel rare earth substituted phosphotungstates containing 5-fluorouracil,K 9(C 4 H 4 FN 2 O 2) 2 Nd(PW 11 O 39) 2 ·25H 2 O(FNdPW) and K 9(C 4 H 4 FN 2 O 2) 2 Ce(PW 11 O 39) 2 ·23H 2 O(FCePW),were synthesized and characterized by elementary analysis,FT-IR spectra,X-ray powder diffraction and 1 H NMR.The thermal analysis showed that FNdPW decomposed at 210 and 493 oC,and FCePW decomposed at 223 and 471 oC,both of which had good thermal stabilities.MTT tests were performed to study the antitumor activities against HeLa cells and HepG-2 cells of FNdPW,FCePW,5-fluorouracil,C 4 H 4 FN 2 O 2 H 2 PW 12 O 40 ·8H 2 O and K 11 Ln(PW 11 O 39) 2 ·xH 2 O(Ln=Nd,Ce),and their cytotoxicities against HEK 293 cells.The results showed that FNdPW and FCePW possessed higher antitumor activities and lower cytotoxicities than those of 5-fluorouracil and C 4 H 4 FN 2 O 2 H 2 PW 12 O 40 ·8H 2 O,of which FNdPW exhibited the highest antitumor activates against HeLa cells(EC 50 =3.41×10-6 mol/L) and HepG-2 cells(EC 50 =6.24×10-6 mol/L).Thus the introduction of rare earth elements and 5-fluorouracil could significantly enhance antitumor effect of polyoxometalates.     

Synthesis and Application of Lanthanide Complexes with Schiff Base of Pridoxylidence-Glycine

Ｔｈｅｈａｒｍｆｕｌｎｅｓｓｏｆｈｅａｖｙｍｅｔａｌｅｌｅｍｅｎｔｓｏｎｐｌａｎｔｓｉｓｏｎｅｏｆｔｈｅｓｅｒｉｏｕｓｅｎｖｉｒｏｎｍｅｎｔａｌｐｒｏｂｌｅｍｓｏｆｔｈｅｍｏｄｅｒｎｗｏｒｌｄ .Ｉｎｒｅｃｅｎｔｙｅａｒｓ ,ｔｈｅｓｔｕｄｙｏｎｔｈｅｍｉｓａｌｓｏｏｎｅｏｆｖｅｒｙａｃ ｔｉｖｅｒｅｓｅａｒｃｈｐｒｏｊｅｃｔｓｉｎｐｌａｎｔｐｏｌｌｕｔｉｏｎｅｃｏｌｏｇｙｆｉｅｌｄｓ[1～ 6 ] .ＬａｎｔｈａｎｉｄｅｃｏｍｐｌｅｘｅｓｗｉｔｈｔｈｅＳｃｈｉｆｆｂａｓｅａｒｅａｃｌａｓｓｏｆｃｏｍｐｏｕ…     

Synthesis, characterization and antitumor activity of rare earth （Y, La） substituted phosphotungstates containing 5-fluorouracil

Two rare earth substituted Keggin-type phosphotungstates containing 5-fluorouracil,K10C4H4FN2O2Y(PW11O39)2·10H2O(FYPW) and K9(C4H4FN2O2)2La(PW11O39)2·18H2O(FLaPW)were synthesized in aqueous solution,and the structures were characterized by Fourier transform infrared spectroscopy(FT-IR),element analysis,inductively coupled plasma spectrometry(ICP),X-ray powder diffraction(XRD) and 1 H nuclear magnetic resonance(NMR).Thermal analysis showed that the decomposition processes of the two compounds could be divided into three steps,the loss of crystal water,the decomposition of 5-fluorouracil unit and the decomposition of Keggin-type polyanions. The in vitro cytotoxicities against HEK 293,HeLa and HepG-2 cells were studied by methyl thiazolyl tetrazolium(MTT)assay.The results showed that FYPW and FLaPW had higher antitumor activities than 5-fluorouracil,C4H4FN2O2H2PW12O40·8H2O and rare earth substituted polyoxometalates K11Ln(PW11O39)2·nH2O(Ln=Y,La).It was concluded that introducing 5-fluorouracil and rare earth(Y or La)into its structure was a considerable way to enhance antitumor activities of polyoxometalates.     

金属间化物（Sm_（1－x）Dy_x）_2Fe_（17）N_y中的各向异性机制探讨

本文主要通过变温穆斯堡尔谱等手段研究金属间化物（Ｓｍ（１－ｘ）Ｄｙｘ）２Ｆｅ（１７）Ｎｙ（ｘ＝０．４；２＜ｙ＜３）的自旋重取向现象，进而对其中的各向异性产生机制进行分析。由实验结果得出Ｄｙ次格子的单轴各向异性较强，导致在１５０Ｋ～１００Ｋ较低温度下出现自旋重取向现象。     

Complexation of N＇- [1-（3-aminophenyl）ethylidine] isonicotinohydrazide with La3＋, Pr3＋, Nd3＋, Sm3＋, Eu3＋ and Gd3＋ ions and associated thermodynamics

A novel Schiff base N′-[1-(3-aminophenyl)ethylidine]isonicotinohydrazide was prepared and its complexation behavior towards some selected lanthanides had been studied employing pH-metric and calorimetric titration and spectral techniques. pH-metric studies were carried out for the trivalent La, Pr, Nd, Sm, Eu, and Gd complexes in 30% aqueous-dioxane medium at constant ionic strength of 0.05 mol/L NaClO4 and at different temperatures of 293, 303 and 313 K. The proton-ligand formation constants of the ligand indicated the presence of only one dissociable proton while the metal-ligand formation constants were compatible with the formation of 1:1 Ln(Ⅲ) complexes. The sta-bility of the complexes followed the order: La3+Gd3+, showing a break at gadolinium. The thermodynamic parame-ters, ΔG, ΔH and ΔS associated with protonation and complexation reactions were negative which suggested that all reactions were exother-mic and enthalpy-driven. Isothermal calorimetric studies of Gd3+-aeINH systems at 303 K also showed exothermic nature of the complexation reaction and formation of 1:1 complex in agreement with the pH-metric data. Formation of 1:1 complexes was confirmed by the characteriza-tion of Nd(Ⅲ) complex. A seven coordinated geometry was assigned for the complex based on its elemental and spectral data.     

Synthesis, Characterization and Fluorescence of Rare earth Nitrate Complexes with Triaza-crown Ether Derivative

Sinceaza crownethershowsspecialcoordinationpropertiestotransitionmetalandheavymetalions[1,2 ] ,therearemanyreportsofthecomplexesinhost guestchemistry ,molecularrecognition[3 ,4] andionophoreinmembranetransportation[5] ,butthereislittlereportontheirrareearthscomplexesandthefluorescenceaboutthecomplexes[6] ,andthefluorescenceintensityoftheircomplexesarenotverystrong .Weinsetbenzoylgroupintothemacrocycle ,expectingthatitsrareearthscomplexeshavebetterfluorescenceproperties .Inthispaperthesynthesis…     

Synthesis, Characterization and Fluorescence Properties of Europium, Terbium Complexes with Biphenyl-4-Carboxylic Acid and o-Phenanthroline

Two series of solid complexes of europium and terbium with biphenyl 4-carboxylic acid and phen were synthesized and characterized in this report. Their elemental analysis, molar conductivities and TG-DTA studies indicate that the complexes have the composition of Eu(phen)L3·1/2H2O, Eu0.5RE0.5(phen)L3·1/2H2O; Tb(phen)L3·H2O and Tb0.5RE0.5(Phen)L3·1/2H2O. (RE=Y3 , La3 and Gd3 ; L=biphenyl 4-carboxylic acid; phen=o-Phenanthroline). The studies of their IR, UV 1H NMR and molar conductivities demonstrate that biphenyl 4-carboylic acid is bounded with RE(Ⅲ) ion. Rare earth ions coordinate with two nitrogen atoms of phen molecules directly in these rare earth complexes. The fluorescence spectra and fluorescence lifetimes of the rare earth complexes show that the fluorescent intensity and lifetime of a series of europium complexes are longer than those of the series of terbium complexes as having the some ligands. There are better fluorescent intensity and lifetime of hetero-nuclear rare earth complexes than homo-nuclear rare earth complexes for europium complexes. The fluorescence emission intensity of Eu3 is raised by inert fluorescent rare earth ions (Y3 , Gd3 and La3 ), but in Tb3 hetero-nuclear rare earth complexes the intensity of Tb3 ions are quenched by the inert fluorescent rare earth ions.     

Thermochemical studies on complex of [Sm(o-NBA)_3phen]_2

A ternary complex [Sm(o-NBA)3phen]2 (o-NBA: o-Nitrobenzoate; phen: 1,10-phenanthroline) was synthesized and characterized by elemental analysis, IR, molar conductance, and thermogravimetric analysis. The dissolution enthalpies of SmCl3·6H2O(s), o-HNBA(s) and phen·H2O(s) in mixed solvent (VHCl :VDMF :VDMSO=2:2:1) were determined by calorimetry at 298.15 K. The enthalpy change of the reaction was determined to be rHmΔθ=252.49±1.60 kJ/mol. Using the relevant data in the literature and a thermochemical recycle according to Hess’s Law, the standard molar enthalpy of formation of [Sm(o-NBA)3 phen]2 (s) was estimated to be f mHΔθ=–4109.2±7.3 kJ/mol.     

Synthesis and Crystal Structure of a 4f-3d Complex [La(DMF)_6(H_2O)_3][Cr(CN)_6]·2H_2O

Ｒｅｃｅｎｔｌｙ ,ｔｈｅｒｅｈａｓｂｅｅｎｃｏｎｓｉｄｅｒａｂｌｅｉｎ ｔｅｒｅｓｔｉｎｌａｎｔｈａｎｉｄｅ(Ⅲ )ｈｅｘａｃｙａｎｏｆｅｒｒａｔｅｓａｎｄｔｈｅａｎａｌｏｇｏｕｓｃｏｂａｌｔ(Ⅲ )ａｓｗｅｌｌａｓｃｈｒｏｍｉｕｍ(Ⅲ )ｃｏｍｐｌｅｘｅｓｂｅｃａｕｓｅｏｆｔｈｅｉｒｐｏｔｅｎｔｉａｌａｓｃａｔａｌｙｔｉｃ ,ｓｅｍｉｃｏｎｄｕｃｔｉｖｅ ,ａｎｄｍａｇｎｅｔｉｃｍａｔｅ ｒｉａｌｓ[1～ 4] .Ｆｏｒｅｘａｍｐｌｅ ,ｍａｇｎｅｔｉｃｓｔｕｄｉｅｓｏｎａｓｅｒｉｅｓｏｆｔｈｒｅｅ ｄｉｍｅｎｓｉｏ…     

Synthesis, Characterization of α-Oxopentanedioic Acid-Isonicotinoyl Hydrazone Rare Earth-Complexes and Relaxivity of Gd-complex

Themagneticresonanceimaging (MRI)tech niqueforthemedicineisveryusefultodiagnosepre tumorandbloodvesseldiseaseinheartandbrainandothermalignantpre diseases .Therefore ,specialatten tionhasbeenalsopaidtoMRIcontrastagents ,whichareindispensablediagnosingdrugsforthemagneticresonanceimagingtechnique[1,2 ] .Gadolinium (Ⅲ)complexwithsomepolycarboxylicandpolyaminelig ands ,suchasGd(DTPA)·nH2 O ,waswidelyusedincliniclongago .OurpreviousworkshowsthatsomepolycarboxylicSchiffbasecomplexeswithrareea…     

Synthesis, characterization, and anticancer properties of rare earth complexes with Schiff base and o-phenanthroline

Five novel ternary complexes of the rare earth ions with o-phenanthroline（Phen） and Schiff base salicylaldehyde L-phenyla- lanine（KHL） were synthesized in ethanol. Their compositions were characterized by elemental analysis, molar conductance, ^1H NMR, FT-IR, and Raman spectra. The formulas of the complexes were verified to be RE（L）（Phen）Cl（H2O） （RE=La^3＋, Ce^3＋, Nd^3＋, Er^3＋, and Gd^3＋; L=Schiff base salicylaldehyde L-phenylalanine; phen=o-phenanthroline）. Methyl thiazolyl tetrazolium （MTT） colorimetry and flow cytometry were used to test the anticancer effect of the complexes with K562 tumor cell. The research showed that the complexes could inhibit K562 tumor cell＇s growth, generation, and induce apoptosis. The inhibition ratio was accelerated by increasing the dosage, and it had significant positive correlation with the medication dosage.     

Synergistic extraction of rare earths by mixture of HDEHP and HEH/EHP in sulfuric acid medium

The extraction of RE（Ⅲ） （RE=La, Nd, Sm, Gd） in sulfuric acid medium using the mixture of HDEHP（H2B2） and HEH/EHP（H2L2） was investigated. The synergistic enhancement coefficient（R） was calculated for La （1.96）, Nd（3.52）, Sm（5.96）, and Gd（5.71）, respectively, at pH=2.0, and it was seen that the R increased with the increase of aqueous quilibrium pH. The configuration of the extracted complexes was considered to be RE（SOa）xH2x（HB2）3 with HDEHP, RE（SOa）xH2x（HL2）3 with HEH/EHP, and RE（HB2）2（HL2） with their mixture as the extractant with the slope method. The equilibrium constants and stability constants were calculated. A cation exchange mechanism was proposed as well.