Synthesis, characterization and enhanced luminescence of terbium complexes with 2-pyrazinecarboxylic acid and butanedioic acid by inert-fluorescent lanthanide ions

Ten solid terbium complexes with 2-pyrazinecarboxylic acid (Hpyca) and butanedioic acid (BDAH) were synthesized via coprecipitation method and characterized by elemental, EDTA titration, inductively coupled plasma (ICP), thermogravimetry-differential scanning calorimetry (TG-DSC) and infrared (IR) analyses. The results showed that the complexes had the compositions of Tb(pyca)(BDA)·2H2O, Tb0.5Y0.5(pyca)(BDA)·2H2O, Tb0.5La0.5(pyca)(BDA)·3H2O, Tb0.5Gd0.5(pyca)(BDA)·2H2O, Tb0.7Y0.3(pyca)(BDA)·3H2O, Tb0.7La0.3(pyca)(BDA)·0.5H2O, Tb0.7Gd0.3(pyca)(BDA)·H2O, Tb0.6Y0.4(pyca)(BDA)·2.5H2O, Tb0.6La0.4 (pyca)(BDA)·2.5H2O and Tb0.6Gd0.4(pyca)(BDA)·3H2O. IR spectra indicated that the rare earth ions coordinated with the carboxylic oxygen atoms of Hpyca and BDAH. Luminescence spectra showed that the doped La3+, Y3+ or Gd3+ ions did not affect the luminescence emission peak positions, but remarkably increased the luminescent intensities of terbium complexes. Furthermore, the doped lanthanide complexes showed longer luminescence lifetimes and higher quantum yields than pure terbium complex. The enhanced luminescence efficiencies of Tb3+ ions in the doped complexes might result from the antenna effect of the two carboxylate ligands as well as the decrease of the self-quench of the Tb3+ ions induced by the doped lanthanide ions.     

Microwave assisted synthesis, spectroscopy and biochemical aspects of lanthanum(Ⅲ) and praseodymium(Ⅲ) complexes with oxadiazole functionalised dithiocarbazinates

The new lanthanum (Ⅲ) and praseodymium (Ⅲ) complexes of the general formula [Ln(L)3] (Ln=La(Ⅲ) or Pr(Ⅲ); LK=potassium salt of dithiocarbazinates) were prepared by both, conventional thermal and by the use of microwave technology. Elemental analyses, elec-trical conductance, magnetic moment and electronic, infrared, far-infrared, 1H and 13C NMR spectral studies were used to characterize the complexes. The molecular weights of few complexes were determined by FAB-mass spectra. Nephelauxetic ratio, covalency parameter and bonding parameter for these complexes were also calculated. The probable structures of the complexes were proposed. The antifungal and antibacterial activities of the complexes were evaluated. The activities were correlated with the structures of the compounds.     

Synthesis and luminescent properties of novel pyrazolone rare earth complexes

A novel pyrazolone pyridine-containing ligand,2,6-bis(1-phenyl-4-ethoxycarbonyl-5-pyrazolone-3-yl)pyridine (H2L) was de-signed and synthesized from pyridine-2,6-dicarboxylic acid (1),and its Eu(III) and Tb(III) complexes were prepared.The ligand and com-plexes were characterized in detail based on FT-IR spectra,1H NMR,elemental analysis and thermal analysis,and the formula of Ln2L3·4H2O (Ln=Eu or Tb) of rare earth complexes was confirmed.The UV-vis absorption spectra and photoluminescence properties of the complexes were investigated,which showed that the Eu(III) and Tb(III) ions could be sensitized efficiently by the ligand (H2L) and emit the photolumi-nescence with high intensity,narrow half-peak width,and monochromic light.The results indicated that the complexes showed potential as excellent luminescent materials.     

Syntheses and Infrared Spectra of Rare Earth Complexes with Diethyl Phosphate

The title complexes Ln(DEP),(Ln=La,Sm,Eu,Ho and Yb)were synthesized by reaction of triethylphosphate with trivalent rare earth chlorides.The mechanism of thermo-decomposition of the complexes hasbeen studied.According to their IR spectra,the residues of the thermo-decomposition of the complexes wereidentified as Ln(PO_3)_3.Their IR spectra were measured and principal IR bands were assigned.The experimentalresults of the IR spectra of the complexes show that the title complexes have the same coordination form and mo-lecular configuration as rare earth,e.g.Sm,complex with dimethyl phosphate(Sm(DMP)_3).Each of the rareearth ion links three rare earth ions nearby through double“O-P-O”bridges to form a special network ofrings-linking-rings,each of which consists of twenty-four atoms.The Ln-O bond is principally ionic.     

Synthesis and spectral characteristics of La2MoO6：Ln3＋ （Ln=Eu, Sm, Dy, Pr, Tb） polycrystals

The novel phosphors of La 2 MoO 6 activated with the trivalent rare earth Ln 3+ (Ln=Eu, Sm, Dy, Pr, Tb) ions were synthesized by solid state reactions at high temperature in air atmosphere, and their phase impurities and luminescent properties were studied. The photoluminescence (PL) excitation and emission spectra, and decay curves were employed to study their luminescence properties. The lifetimes of the characteristic emissions from Ln 3+ ions were in the order of millisecond except Pr 3+ ions. (LaEu 1-x ) 2 MoO 6 was a promising phosphor for practical application and the optimum concentration was x=0.075. The concentration quenching mechanism of Eu 3+ was also discussed by theoretical fitting using Burshtein model.     

Synthesis and Properties of Heteropoly Complexes LnHSiW_(12)O_(40)·xH_2O

The present paper covers seven rare earth-containing tungstosilicate heteropoly complexesLnHSiW_(12)O_(40)·xH_2O with Keggin structure(Ln=La,Ce,Pr,Nd,Sm,Eu and Gd)snythesized by doubledecomposition reaction.The synthesized heteropoly complexes were characterized by ICP,~(29)Si-NMR,XPS,XRD,IR,UV,polarogram,CV and TG-DTA.The relationship between the structure of the synthesizedheteropoly complexes and their properties is discussed.     

Preparation and Properties of Rare Earths with 6-Methyl-2-Picolinic Acid N-Oxide and 2,2'-Bipyridine-N,N'-Dioxide

A series of new ternary complexes of 6-methyl-2-picolinic acid N-oxide(HL) and 2,2'-bipyridine-N,N'-dioxide(bipyO2) with Ln3+(Ln=La, Sm, Eu, Gd, Tb, Dy, Yb) were synthesized and characterized. The composition of the ternary complexes is determined as {LnL3·bipyO2·H2O} (n-1)H2O (n=2.5～3.0). They are nonelectrolytes in ethanol. It is found that fluorescence intensities of the ternary complexes, LnL3·bipyO2·H2O, are weaker than those of binary complexes, LnL3·H2O. And it is also found that Tb3+ luminescence at 489.3 nm in TbL3·bipyO2·H2O is sensitized by bipyO2, and it is stronger than that at 543.8 nm, Which differs from TbL3·H2O.     

Luminescence study of europium(III) tris(β-diketonato)/phosphonate complexes in chloroform

The extraction of Eu(III) with β-diketone, HA, and monodentate or bidentate Lewis bases, B, into chloroform and the luminescence properties of the extracted species were studied. Pivaloyltrifluoroacetone, Hpta, and 2-thenoyltrifluoroacetone, Htta, were used as the β-diketones. The Lewis bases, B, were tetraethyl methylene diphosphonate, POPO, which was bidentate, and diethyl benzylphosphonate, PhPO which was monodentate. Based on the extraction data, the stability constants, log β of the first complexes between tris(β-diketonato)Eu(III) and the phosphonate, EuA3B, were determined to be 6.0 for the POPO complex and 3.40 for the PhPO complex. The Eu(III) luminescence intensity in the EuA3POPO was larger than EuA3 where A was either pta or tta at similar concentrations of Eu(III), while that in Eu(pta)3PhPO was stronger than EuA3; however, in Eu(tta)3PhPO, it was weaker than Eu(tta)3. The POPO functions as a sensitizer, and the PhPO functions as a quencher for the tta chelate and as a sensitizer for the pta chelate. From the lifetime and quantum yield, φ, of the Eu(III) luminescence in the complexes as well as the observation of the extractability of Eu(III) with the Hpta and the phosphonates and of the luminescence spectra of the complexes, it was confirmed that the extraction of Eu(III) was remarkably enhanced with a β-diketonate and a strong Lewis base, and also the ternary complex that was formed as the extracted species, showed luminescence enhancement. This phenomenon may be due the formation of a strong bond between the Eu(III) and the strong Lewis base leading to more hydrophobicity in the extracted species and also to more effective energy transfer from the Lewis base to the Eu(III). It was not significant whether the donor atoms were N or O.     

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

Two three-dimensional complexes Ln(DMPA)3phen2(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.     

Metal-organic frameworks of lanthanide iminodiacetates and tartrates:Synthesis,structural characterization and luminescence properties——Commemorating the 100th anniversary of the birth of Academician Guangxian Xu

Two series of lanthanide-containing metal-organic frameworks(Ln-MOFs) of the general formula{[Ln(HIDA)_2 H_2 O]ClO_4·H_2 O}_n(Ln = La(1),Nd(2),Eu(3),Gd(4),Tb(5),Eu:Tb(6);H_2 IDA=iminodiacetic acid) and [Ln(TT)(HTT)(H_2 O)_3]_n(Ln=Eu(7),Gd(8),Tb(9),Dy(10),and Eu:Tb(11);H_2 TT=tartaric acid)were synthesized by reacting Ln(ClO_4)_3 with iminodiacetic acid and L-tartaric acid,respectively.All compounds were structurally characterized by single-crystal X-ray diffraction.Elemental analyses are co nsistent with the corre sponding crystallographically generated formulas.Mo reover,the luminescence properties of both the single and mixed-lanthanide complexes were studied.Near infrared,red,and green emissions that are characteristic of Nd(Ⅲ),Eu(Ⅲ),and Tb(Ⅲ) are observed for 2,3/7,and 5/9,respectively.For the two mixed-lanthanide complex systems 6 and 11,depending on the relative amount of Eu(Ⅲ) and Tb(Ⅲ),the color of emission can be fine-tuned.It is found that a small amount of Eu(Ⅲ) is adequate for the observation of the most intense transition of Eu(Ⅲ).This is believed to be a result of energy transfer from Tb(Ⅲ) to Eu(Ⅲ) within the same complex-a conclusion supported by the significantly shortened lifetime of Tb(Ⅲ) and the accompanying enhanced lifetime of Eu(Ⅲ) in the mixedlanthanide complex with respect to the corresponding values for the pure Tb(Ⅲ) and Eu(Ⅲ) complexes with the same ligand.     

Solid state reaction synthesis and total electrical conductivity of La_(0.7)Sr_(0.3)Cr_yMn_zCo_(1-y-z)O_(3-δ)

The La0.7Sr0.3CryMnzCo(1-y-z)O3-δ samples were prepared by solid state reaction.The phases,microstructure and properties of the samples were investigated by XRD,SEM,DC four-probe method and iodometry method.The single orthorhombic phase La0.7Sr0.3CryMnzCo(1-y-z)O3-δ perovskite oxides were obtained when sintered at l350 °C for 10 h.The oxygen nonstoichiometry of the materials varied inversely with the total electronic conductivity.The sample with composition of La0.7Sr0.3Cr0.5Mn0.35 Co0.15O3-δ had the maximal total electronic conductivity and the lowest oxygen nonstoichiometry which were 22.4 S/cm and 0.040 at 850 °C,respectively.The low total electronic conductivity is related to the low relatively density of the samples directly.The activation energy of conduction changed at 550 °C,and the activation energy of conduction at high temperature(T550 °C) was higher than that at low temperature range(T550 °C).     

Synthesis and photoluminescence studies of Ba(Gd,Ln)B9O16:Eu3+(Ln=La,Y) phosphors for n-UV LED lighting and display devices

BaGdB9O16:Eu3+ and Ba(Gd,Ln)B9O16:Eu3+(Ln=La, Y) phosphors were synthesized by solid state diffusion method. The X-ray diffraction, scanning electron microscopy(SEM) and photoluminescence properties were investigated. The as-synthesized BaGdB9O16:Eu3+ and Ba(Gd,Ln)B9O16:Eu3+(Ln=La, Y) phosphors showed strong red emission under ultraviolet light excitation. By partially substituting Gd3+ by La3+ and Y3+ ions in the host BaGdB9O16:Eu3+ materials, the maximum emission intensity was observed for the optimum composition of BaGd0.91La0.8B9O16Eu0.01 phosphor. The experimental results indicated that the Eu doped BaGdB9O16 and Ba(Gd,Ln)B9O16(Ln=La, Y) phosphors were promising red phosphors, which might find potential applications in near-UV excited LED lighting as well as display devices. Comparison of as-synthesized phosphors with standard phosphor used in CFL(compact fluorescent lamp) was also done. Energy transfer mechanism of Gd3+ to Eu3+ was also discussed in this paper.     

Preparation and luminescent properties of CaAl_2O_4:Eu~(3+),R~+(R=Li,Na,K) phosphors

CaAl2O4:Eu3+,R+(R=Li+,Na+,K+) red phosphors were synthesized by solid state reaction method.X-ray diffraction(XRD) and photoluminescence(PL) were employed to characterize their structural and luminescent properties.It was found that the optimal sintering temperature and sintering time were 1200 °C and 4 h,respectively.The optimal concentration of doped Eu3+ was 3 mol.%.Furthermore,under ultraviolet excitation with a wavelength of 254 nm,these samples showed red luminescence which were probably attributed to the transitions from 5D0 excited state to 7FJ(J=0-4) ground states of Eu3+ ions.The feature and the high intensity of hypersensitive transition from 5D0→7F2 indicated that Eu3+ preferred to occupy a low symmetry site.The incorporation of alkali metal ions greatly enhanced the luminescence intensity probably due to the influence of charge compensation of alkali metal ions.     

Thermal Stability and Luminescence Properties of Eu^3＋ and Tb^3＋ Complexes with a Silica Matrix by Sol-Gel Method

Ternary complexes of europium and terbium with benzoic acid and 1, 10-phenanthroline [RE(BA)3phen] (BA=benzoate phen=1,10-phenanthroline) were introduced into a silica matrix by sol-gel method. The thermal stability and luminescence behavior of the complexes in silica gels were studied in comparison with the corresponding solid-state complexes by thermal decomposition, excitation and emission spectra. The thermal stability of the complexes is enhanced in silica gel matrix and the luminescence remaines unchanged.     

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.     

Photoluminescence and electrochemiluminescence studies of chosen rare earths systems

Eu（Ⅲ） complexes with chosen Keggin polyoxomatalates, POM, containing organic counter cations （tetrabutylarnmonium, tetrabutylphosphonium, triphenylethylphosphonium）, were synthesized, and their photophysical properties were studied. The synthesized complexes had the general formula of XnH5-n[EuSiW11O39], formulated based on the results of elemental and thermogravimetric analysis and FTIR spectroscopy. The photophysical properties of the obtained compounds were investigated using photoluminescence and electrochemiluminescence, ECL, methods in solutions and solids. The most intense luminescence of Eu（Ⅲ） was observed for the complexes with tetrabutylarnmonium cations. After the addition of phenanthroline to the XnH5-n[EuSiW11O39] solutions, a large increase in the Eu（Ⅲ） luminescence intensity and a lengthening of its luminescence lifetime were observed as a result of the formation of ternary complexes. Attempts to apply ECL as a method of light emission by generating species capable of forming excited states in Ln/POMs, i.e., Tb（Ⅲ） and Eu（Ⅲ） in the Na9EuW10O36 and Na9TbW10O36 complexes, were made. The influence of the POM complexes on the ECL was also tested using the Tb/EDDHA （EDDA=ethylenediamine di（o-hydroxyphenylacetic acid）） complex, which is effective in generating ECL.     

Synthesis,characterization and thermolysis of lanthanide metal nitrate complexes with 1, 10-phenanthroline,Part-95

The nitrate complexes of cerium, praseodymium and neodymium with 1,10-phenanthroline(phen) of general formula [Ln(phen)2(NO3)2(H2O)2]·NO3(where, Ln=Ce, Pr and Nd) were prepared and characterized by X-ray crystallography. Thermolysis of these complexes was investigated by simultaneous thermogravimetry(TG) and differential thermal analysis(DTA). Isothermal TG was taken to evaluate the kinetic parameters using model fitting as well as model free isoconversional methods. The thermolytic pathways were also suggested, which involves decomposition followed by ignition. All the three complexes had coordination number ten and showed multistep decompositions. In order to evaluate the response of rapid heating, ignition delay(Di) measurements were undertaken. The activation energies for ignition were found to decrease in the order: NdPrCe.     

Photoluminescence properties of dinuclear lanthanide complexes in visible and near-infrared region

Several dinuclear lanthanide complexes of Ln2(HTH)6TPPHZ (Ln=Eu, Sm, Er, Nd, Yb, Ho; TPPHZ=Tetrapyrido (3,2-a:2',3'-c:3',2"-h:2"',3'"-j) phenazine; HTH=4,5,5,6,6,6-heptafluroro-1-(2-thienyl)hexane-1,3-dione were synthesized and their photoluminescence properties were investigated. After ligand-mediated excitation, all the complexes showed the characteristic luminescence of the corresponding Ln(III) ions in the visible and NIR regions attributed to energy transfer from the ligands to the metal center. For Eu...     

Synthesis, structure and spectroscopic studies of europium complex with S（＋）-mandelic acid

The Eu3+ complexes with S(+) -mandelic acid were synthesized in the form of powders by mixing aqueous solutions of EuCl3,S(+) -mandelic acid and NaOH in different molar ratios.The powders were characterized by elemental analysis,X-ray powder diffraction(XRPD) method,Fourier transform infrared(FTIR) and Raman spectroscopy,UV-vis reflectance and luminescence spectra as well as lumi-nescence lifetime measurements.It was found that all studied powders of Eu3+ complexes with S(+) -mandelic acid were isostructural and crystalline and formed compounds with the formula Eu(Man) 3(H2O) 2.     

Electrical Properties and Microwave Synthesis of Mixed Rare Earth Oxide Ln0.7Sr0.3-xCaxCo0.9Fe0.1O3-δ

In order to lower the raw materials cost and develop a novel cathode materials for intermediate temperature solid oxide fuel cell(ITSOFC), using mixed rare earth replacing the expensive pure La2O3 as the raw materials, the powders of Ln0.7Sr0.3-xCaxCo0.9Fe0.1O3-δ (Ln=the mixed rare earth, x=0.05, 0.10, 0.15) for the applications as the cathode materials were prepared by microwave sintering process. The crystal structure and the particles morphology of the obtained powders were characterized by XRD and SEM, the electrical conductivity of all samples sintered at 1200 ℃ for 3 h was also measured as the function of the temperature from 100 to 800 ℃ by DC four-probe method in air. The experimental results show that due to the influence of mixed rare earth the powders of Ln0.7Sr0.3-xCaxCo0.9Fe0.1O3-δ synthesized at 1200 ℃ for 0.5 h with the mean particle size of 1～20 μm was of perovskite and cubic fluorite phase as well a little SrO phase, the electrical conductivity of the samples decreases with the adding Ca2+ content, and are all higher than 100 S·cm-1 from 500 to 700 ℃ when x≤0.10. Ln0.7Sr0.3-xCaxCo0.9Fe0.1O3-δ. Can meet the demand of the electrical properties for the cathode materials in ITSOFC.