Optical analysis and separation of trivalent lanthanides in deep eutectic solvents

Deep eutectic solvents(DESs) were used for luminescence measurements in quantitative analysis of trivalent lanthanide ions and as solvents for light rare earth elements(LREE) in solid-liquid separation.The spectroscopic characteristics of lanthanide chlorides LnCl_3(Ln=Eu,Tb),respectively their aquo complexes,are described in a comprehensive study that demonstrates the significant enhancement of the phosphorescence emission intensity in DESs as polar and weakly coordinating solvent.Several DESs stabilize the lanthanide ion luminescence against changes in temperature and moisture,which is advantageous compared with the use of ionic liquids.Small amounts of water lead in certain eutectic systems even to a further increase in phosphorescence emission intensity.By investigating the solubility of lanthanide sesquioxides Ln_2 O_3(Ln=La,Nd,Sm,Eu,Gd,Tb,Dy) in DESs,selectivities are identified that may be of use for the separation of LREE.     

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,characterization, biological activities and luminescent properties of lanthanide complexes with [2-thiophenecarboxylic acid, 2-(2-pyridinylmethylene)hydrazide] Schiff bases ligand

A Schiff base L [2-thiophenecarboxylic acid, 2-(2-pyridinylmethylene)hydrazide] with its lanthanide metal complexes was synthesized. These complexes were characterized by elemental analysis, molar conductivity measurements, spectral analysis(NMR, FT-IR, and UV-Vis), luminescence and thermal gravimetric analysis. The Schiff base ligand was a tridentate chelate and coordinates to the central lanthanide ion with 1:2 metal:ligand ratio. The conductivity data showed a 1:1 electrolytic nature with a general formula [LnL_2(NO_3)_2]NO_3. The luminescence emission properties for Sm, Tb, and Eu complexes were observed and showed that the ligand L could absorb and transfer energy to Sm(III), Tb(III) and Eu(III) ions. The complexes possessed a good antibacterial activity against different bacterial strains. In addition, the scavenging activity of the Ln(III) complexes on DPPH was concentration dependant and the complexes were significantly more efficient in quenching DPPH than the free Schiff base ligand.     

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.     

New Opportunities for Lanthanide Luminescence

Trivalent lanthanide ions display fascinating optical properties. The discovery of the corresponding elements and their first industrial uses were intimately linked to their optical properties. This relationship has been kept alive until today when many high-technology applications of lanthanide-containing materials such as energy-saving lighting devices, displays, optical fibers and amplifiers, lasers, responsive luminescent stains for biomedical analyses and in cellulo sensing and imaging, heavily rely on the brilliant and pure-color emission of lanthanide ions. In this review we first outlined the basics of lanthanide luminescence with emphasis on f-f transitions, the sensitization mechanisms, and the assessment of the luminescence efficiency of lanthanide-containing emissive molecular edifices. Emphasis was then put on two fast developing aspects of lanthanide luminescence: materials for telecommunications and light emitting diodes, and biomedical imaging and sensing. Recent advances in NIR-emitting materials for plastic amplifiers and waveguides were described, together with the main solutions brought by researchers to minimize non-radiative deactivation of excited states. The demonstration in 1999 that erbium tris(8-hydroxyquinolinate) displayed a bright green emission suitable for organic light emitting diodes (OLEDs) was followed by realizing that in OLEDs, 25% of the excitation energy leads to singlet states and 75% to triplet states. Since lanthanide ions are good triplet quenchers, they now also play a key role in the development of these lighting devices. Luminescence analyses of biological molecules are among the most sensitive analytical techniques known. The long lifetime of the lanthanide excited states allows time-resolved spectroscopy to be used, suppressing the sample autofluorescence and reaching very low detection limits. Not only visible lanthanide sensors are now ubiquitously provided in medical diagnosis and in cell imaging, but the feasibility of using NIR emission of ions such as YbⅢ is now being tested because of deeper penetration in biological tissues.     

Raman spectra of RE2O3 （RE=Eu,Gd, Dy,Ho, Er,Tm, Yb,Lu, Sc and Y）：laser-excited luminescence and trace impurity analysis

Raman spectra of a series of cubic rare earth sesquioxides RE2O3 （RE=Eu, Gd, Dy, Ho, Er, Tm, Yb, Lu, Sc and Y） were investigated by Raman spectroscopy with both 532 and 785 nm laser lines. Abundant additional bands due to laser-excited lumines-cence were observed. For Eu2O3, Dy2O3, Ho2O3, Er2O3, Tm2O3 and Yb2O3, the luminescence mainly came from the intrinsic trivalent lanthanide ions, while for Gd2O3, Lu2O3, Sc2O3 and Y2O3, their luminescence were attributed to the trace impurities of other lumines-cent lanthanide ions such as Eu3＋, Nd3＋and Er3＋. This investigation confirmed Raman spectroscopy as a useful tool for detecting trace luminescent lanthanide impurities.     

Crystal Structure and Luminescence Property of Lanthanide Complexes with 2-Fluorobenzoic Acid and 2,2''-Bipyridine

The two compounds of [Ln(2-FBA)3·2,2'-bpy]2 (2-FBA=2-fluorobenzoato, 2,2'-bpy=2,2'-bipyridine, Ln=Eu(1), Dy(2)) were synthesized and their structures were determined by X-ray diffraction method. Crystallized complexes 1 and 2 are isomorphous, monoclinic system with P21/n space group. The two complexes are binuclear molecule with an inversion center. The two lanthanide ions are linked by four bridged 2-FBA ligands and each lanthanide ion is further bonded to one chelated bidentate 2-FBA ligand and one 2,2'-bipyridine molecule. The coordination number of metal ion is eight. The europium complex exhibits strong red fluorescence. 5D0→7Fj (j= 1～4) transition emission of Eu3 ion was observed.     

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.     

Photoluminescence of SrGdGa_3O_7∶RE (RE=Ce~(3 ), Pr~(3 ), Tb~(3 )) under VUV-UV Excitation

SrGdGa3 O7belongstothelargefamilieswhosegeneralchemicalformulaisAMM′3 O7(A =Ca ,Sr ,Ba ;M =La ,Gd ,Y ;M′ =Al,Ga) .Thesecom poundshavemelilitestructure .Structuralinvestiga tionsindicatethatSrGdGa3 O7formstetragonalcrystalswithspacegroupP 4 2 1m .Theunit…     

Synthesis,characteristic and intramolecular energy transfer mechanism of reactive terbium complex in white light emitting diode

A reactive Tb(III) complex with 2-aminobenzoic acid(2-ABAH) and acrylonitrile(AN) as ligands was synthesized.The structure of the complex was characterized by elemental analysis and Fourier transform infrared spectrometry(FT-IR).The results indicated that the ligands were coordinated with Tb(III) ion.Thermal gravity-derivative thermogravimetric(TG-DTG) analysis indicated that the complex kept stable up to 198 oC.Luminescence properties were investigated by UV-vis absorption spectra and fluorescence spectra.The results suggested that being excited at 361 nm,the complex exhibited characteristic emission of Tb(III) ion,revealing that the complex could be excited by 365 nm ultraviolet chip.The HOMO and LUMO,ΔE(HOMO-LUMO),molecular frontier orbital,and the singlet state and triplet energy state levels of the ligands were calculated at the B3LYP/6-31+G(d) level.The results indicated that intramolecular energy transfer mechanism followed Dexter exchange energy transfer theory.Both the calculation for excited state of ligand and energy transfer mechanism could provide the theoretical basis for the design of high luminescent materials of rare earth complexes with organic ligands.     

Effect of acceptor ions concentration in lead phosphate glasses co-doped with Tb~(3+)-Ln~(3+)(Ln=Eu,Sm)for LED applications

In this work,lead phosphate glasses doubly doped with Tb~(3+) and Ln~(3+)(Ln=Eu,Sm) ions were prepared.The excitation and emission spectra of lanthanides ions were recorded.The luminescent properties of lead phosphate glasses containing various concentrations of acceptor ions were analyzed.It is observed that luminescence bands corresponding to characteristic transitions of rare earth ions are present on emission spectra measured under direct excitation of Tb~(3+).From the emission spectra,the Commission Internationale de I'Eclairage(CIE) chromaticity coordinates(x,y) were calculated in relation to potential application studied systems for white LEDs.Luminescence lifetimes were also determined based on decay measurements and discussed in details.In general,the luminescence spectra and luminescence lifetimes depend on the relative concentrations of the optically active dopants.     

Use of sensitized luminescence of lanthanides in analysis of drugs

The sensitization of the Tb(III) and Eu(III) ions luminescence by drugs, the pyrocatechol, naphthyridine and heterocyclic aromatic acid derivatives, were studied. It was shown that a result of intramolecular energy transfer from the ligand molecule to the lanthanide ion increases the luminescence intensity of the latter by 10(8)-10(10) times. The luminescence properties of the complexes in solutions were investigated. The highly sensitive methods for luminescence determination of dopegyt, levodopum, dophaminum, nevigramon, furosemidum and cinchophenum were developed. The detection limits of the drugs are 0.0005, 0.02, 0.5, 0.01, 0.05 and 0.1, respectively.     

Synthesis,crystal structures of novel complexes of rare earth with norfloxacin,interaction with DNA and BSA

Three novel rare earth complexes [N(CH 3) 4 ][Ln(NF) 4 ]·6H 2 O(Ln=Nd(III)(1),Sm(III)(2),Ho(III)(3)) were synthesized using hydrothermal method from norfloxacin HNF=1-ethyl-6-fluoro-1,4-dihydro-4-oxo-7-(1-piperazinyl)-3-quinoline carboxylic acid,C 16 H 18 FN 3 O 3),imidazole and rare earth nitrates.The complexes were characterized by elemental analysis,FT-IR,TG-DTG and X-ray single crystal diffraction.Each rare earth ion was eight-coordinated with carboxyl-O atoms and keto-O atoms from norfloxacin.Four of the norfloxacin ions acted as bidentate chelate group took part in the coordination with rare earth ion.The structures of complexes were tetragonal system with space group I4 1 /acd,which were allomerism.The interaction between complex 1 and DNA was studied by electronic absorption spectra and fluorescence spectroscopy.The binding interaction between the complex 1 and bovine serum albumin(BSA) was studied by fluorescence spectroscopy.The complex 1 bound to DNA by the mode of partial intercalation.Complex 1 had a strong ability to quench the fluorescence from BSA.The complex interaction was mainly a static quenching process with BSA together with formation of two binding sites.     

邻氨基苯甲酸-联吡啶-混合稀土(Eu、Tb)配合物的荧光研究

:研究用邻氨基苯甲酸铵、2 ,2’-联吡啶与氯化铕、氯化铽在水 -乙醇溶液中反应合成了邻氨基苯甲酸- 2 ,2’-联吡啶 -铕铽异核稀土配合物 ,并测定了配合物的红外光谱。红外光谱数据表明 :邻氨基苯甲酸中的羧基和氨基均与稀土离子配位 ,联吡啶中的氮也与稀土离子配位 ;由元素分析数据推测 ,配合物的化学组成式为(Eux Tb1 - x) L3L′(其中 L 为邻氨基苯甲酸 ,L′为 2 ,2’-联吡啶 ) ;在 35 1nm紫外光激发下 ,研究了配合物的荧光光谱 ,结果表明 ,Eu3 的荧光发射被 Tb3 强烈敏化 ,而 Tb3 的荧光发射被 Eu3 离子强烈猝灭     

Studies on synthesis and fluorescent property of rare earth complexes RE（ABMF）2AA and copolymers RE（ABMF）2AA-co-MMA

Four new complexes RE(ABMF)2AA (RE=Sm, Eu, Tb, Dy) were synthesized by the reaction of RECl3·6H2O with acrylic acid (HAA) and 1-(2-furyl)-3-phenyl-1,3-propanedione (ABMF). The copolymerization of the rare earth complexes with methyl methacrylate was studied by using 2,2-azobis-isobutyronitrile as an initiator. The composition and structure of the four complexes were characterized by elemental analysis, UV-vis and FTIR. The glass transition temperature and molecular weight of the copolymers were determined. Photoluminescent measurement showed that ligand ABMF could efficiently transfer the energy to Sm3+ and Eu3+ ions in the complexes and sensitize the luminescence of the rare earth ions, but could not sensitize Tb3+ and Dy3+ ions. As a result, both Sm3+ and Eu3+ complexes emitted the characteristic fluorescence of Sm3+ and Eu3+ ions due to the f-f transitions. The four copolymers could emit strong fluorescence of the rare earth ions.     

Synthesis,characterization and fluorescence properties of a novel rare earth complex for anti-counterfeiting material

A novel ligand with two ester groups, two benzene rings and two carboxyl groups was synthesized. The composition and structure of the ligand were characterized by the Fourier transform infrared spectroscopy (FT-IR), nuclear magnetic resonance spectrum (NMR) and UV spectrometer. The rare-earth complex with the ligand and 1, 10-phenanthroline (phen) was synthesized and structurally characterized by FT-IR, TG and fluorescent spectrometer. The results showed that the novel multicarboxyl ligand could efficiently transfer the energy to Eu³⁺ ions in the complex and sensitize the luminescence of the rare earth ions, and the complex could emit strong fluorescence of the rare earth ions.     

Synthesis,characterization and fluorescence properties of a novel rare earth complex for anti-counterfeiting material

A novel ligand with two ester groups,two benzene rings and two carbox yl groups was synthesized. The composition and structure of the ligand were char acterized by the Fourier transform infrared spectroscopy(FT-IR) ,nuclear magnet ic resonance spectrum(NMR) and UV spectrometer. The rare-earth complex with the ligand and 1,10-phenanthroline(phen) was synthesized and structurally charact erized by FT-IR,TG and fluorescent spectrometer. The results showed that the no vel multicarboxyl ligand could efficiently transfer the energy to Eu3+ ions in t he complex and sensitize the luminescence of the rare earth ions,and the comple x could emit strong fluorescence of the rare earth ions.     

Preparation and Luminescence Properties of LB Films Based on 4-Hexadecyloxybenzoic Terbium

LB films of 4-hexadecyloxybenzoic-terbium by using the subphase containing Tb^3 were prepared. The mono-layer behavior of 4-bexadecyloxybenzoic acid (HOBA) on the subphase containing rare earth ions was studied. IR and UV spectra show that the rare earth ions were bound to carboxylic acid head groups and the coordination took place between the polar head group and the rare earth ions. The luminescence spectra show that the LB films have the fine luminescence properties, and the LB films emit strong luminescence under UV light irradiation.     

Preparation,Photo and Electroluminescence Properties of Novel Rare Earth Aromatic Carboxylates

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有机碱在铕-二苯甲酰甲烷配合物中的协同发光效应研究

合成了铕－ 二苯甲酰甲烷（ Ｄ Ｂ Ｍ） ,铕－ Ｄ Ｂ Ｍ － 有机碱系列配合物,常温下研究了它们的固态荧光光谱,发现有机碱对 Ｅｕ － Ｄ Ｂ Ｍ 配合物有 明显的协同发光效应,得到了高光效的鲜红色荧光材料 Ｅｕ － Ｄ Ｂ Ｍ － Ｃ Ｐ,并探讨了有关协同发光机理。