Luminescent Properties of Bi-Rare Earth Complexes with m-methylbenzoic Acid and 1, 10-phenanthroline

Ｔｈｅｒｅｈａｓｂｅｅｎａｇｒｏｗｉｎｇｉｎｔｅｒｅｓｔｉｎｔｈｅｌｕｍｉｎｅｓｃｅｎｃｅｐｒｏｐｅｒｔｉｅｓｏｆｌａｎｔｈａｎｉｄｅｃｏｍｐｌｅｘ ｅｓｗｉｔｈｏｒｇａｎｉｃａｃｉｄｓ ,ｓｕｃｈａｓａｒｏｍａｔｉｃａｃｉｄｓｏｒｐｈｔｈａｌｉｃａｃｉｄｓｂｅｃａｕｓｅｏｆｔｈｅｉｒｐｏｔｅｎｔｉａｌｃｈｅｍｉｃａｌａｎｄｂｉｏｌｏｇｉｃａｌａｐｐｌｉｃａｔｉｏｎｆｏｒｐｒｏｂｅｓａｎｄｌａｂｅｌｓ .Ｅｕ3 + ａｎｄＴｂ3 + ｈａｖｅｍｏｒｅｅｘｃｅｌ ｌｅｎｔｌｕｍｉｎｅｓｃｅｎｃｅｐｒｏｐｅｒｔｉ…     

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.     

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.     

Influence of La, Y, Gd, Cu, NH4^＋ Ions and DMSO on Luminescent Property of Terbium Complexes with Sulfosalicylate

Ｔｈｅｌａｎｔｈａｎｉｄｅｃｏｍｐｌｅｘｅｓｏｆｏｒｇａｎｉｃｌｉｇ ａｎｄｓａｓｆｌｕｏｒｅｓｃｅｎｔｍａｔｅｒｉａｌｓｈａｖｅｒｅｃｅｉｖｅｄｅｘ ｔｅｎｓｉｖｅａｔｔｅｎｔｉｏｎ .Ｔｈｅｕｓｅｏｆｆｌｕｏｒｅｓｃｅｎｔｏｒｇａｎｏ ｌａｎｔｈａｎｉｄｅｃｏｍｐｌｅｘｅｓｒｅｑｕｉｒｅｈｉｇｈｆｌｕｏ ｒｅｓｃｅｎｃｅｉｎｔｅｎｓｉｔｙａｎｄｌｏｗｃｏｓｔｃｏｍｐｌｅｘｅｓ .Ｉｎｒｅｃｅｎｔｙｅａｒｓ ,ｔｈｅｆｌｕｏｒｅｓｃｅｎｃｅｅｎｈａｎｃｅｍｅｎｔｏｆＴｂ(Ⅲ )ｏｒＥｕ(Ⅲ )ｃｏｍｐｌｅｘｅ…     

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 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-phenanthroline, 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 room 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.     

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.     

Luminescent and Thermal Properties of Sm^ 3＋ Complex with Salicylate and o-Phenanthroline Incorporated in Silica Matrix

A ternary Sm（ Ⅲ ） complex with salicylate （sal-） and o-phenanthroline （phen） was synthesized and incorporated in silica matrix by sol-gel method. The luminescence behavior of the complex in silica gel was studied compared with that of the pure complex by means of emission, excitation spectra and thermogravimetic analysis. The results indicate that the fluorescence intensity ratio of the ^4G5/2→^6H9/2 transition to the ^4G5/2→^6H5/2 transition in silica gel doped with Sm（sal）3 （phen） is lower than that of the pure Sm（sal）3（phen）. The thermal stability of Sm（sal）3（phen） is enhanced greatly by the introduction of the complex into silica matrix. An isolated and chemical inert environment of the complex appears to be responsible for the thermal stability enhancement in silica gel.     

Sol-Gel Assembly and Luminescence of SiO2／PEMA Hybrid Material Incorporated with Terbium Complex

Ｔｈｅｓｏｌ ｇｅｌｍｅｔｈｏｄｈａｓｂｅｅｎｓｈｏｗｎｔｏｂｅａｓｕｉｔａｂｌｅａｐｐｒｏａｃｈｆｏｒｔｈｅａｓｓｅｍｂｌｙｏｆｎｏｖｅｌｌｕｍｉｎｅｓｃｅｎｔｍａｔｅｒｉａｌｓ[1 ,2 ] .Ｐｈｏｔｏａｃｔｉｖｅｒａｒｅｅａｒｔｈｏｒｇａｎｉｃｃｏｏｒｄｉｎａｔｉｏｎｃｏｍｐｏｕｎｄｓ ,ｓｕｃｈａｓｅｕｒｏｐｉｕｍａｎｄｔｅｒｂｉｕｍｃｈｅｌａｔｅｓｗｉｔｈｏｒｇａｎｉｃｌｉｇａｎｄｓｅｘｈｉｂｉｔｉｎｔｅｎｓｅｎａｒｒｏｗｂａｎｄｅｍｉｓｓｉｏｎｓｖｉａａｎｅｆｆｅｃｔｉｖｅｅｎｅｒｇｙｔｒａｎ…     

A series of rare earth coordination polymer constructed from paddle-wheel building blocks

Three coordination polymers, Ln2（bpdc）3（phen）2（H2O）2 （Ln=Nd（1）, Eu（2）, and Tb （3）; bpdc=2,2＇-bipyridine-3,3＇-dicarboxylate; phen=1,10-phenanthroline）, were obtained by hydrothermal reaction of Ln2O3 with 2,2＇-bipyridine-3,3＇-dicarboxylate acid, and 1,10-phe- nanthroline. They were characterized by single-crystal X-ray diffraction, IR spectra, and photoluminescent spectra. The crystallographic data of 1-3 indicated that they were isostructural. Both complexes contained paddle-wheel building blocks, formed by bpdc and phen ligands. These paddle-wheel secondary building units （SBUs） were further connected to form two-dimensional （2-D） metal organic framework （MOF） networks by 2,2＇-bipyridine-3, and 3＇-dicarboxylate tinkers. A three-dimensional （3-D） supramolecular structure was formed by π-π aromatic interactions between adjacent 2-D infinite networks. Photoluminescent measurements indicated that europium compound 2 and terbium compound 3 were strong, red and green emitters, respectively.     

Synthesis and characterization of terbium（Ⅲ）-pyromellitic acid（H4L）-1,10-phenanthroline （phen） luminescent complex

The terbium(Ⅲ)-pyromellitic acid(H4L)-1,10-phenanthroline(phen) luminescent complex was synthesized using a co-precipitation method.The chemical composition of the synthesized complex was speculated to be Tb4L3(phen)0.075·10H2O by elemental analysis,inductively coupled plasma-atomic emission spectroscopy(ICP-AES),and Fourier-transform infrared spectroscopy(FT-IR).The X-ray diffraction analytic results indicated that the synthesized complex is a new crystalline complex,whose structure was different from those of other two ligands.The scanning electron microscopy analytic results showed that the product was of spherical crystals with good dispersion property,and the mean diameter of the spheres was about 1-2 μm.The TG-DTA result showed that the complex had good stability below 489 °C.PL spectra showed that the complex emitted characteristic green fluorescence of Tb(Ⅲ) ion under ultraviolet excitation.     

Luminescent Properties of A Novel Terbium Complex Tb（o-BBA）3（phen）

A novel rare earth complex of terbium ion with 2-benzoylbenzoic acid and 1, 10-phenathroline （Tb（o-BBA）3 （phen）, o-BBA-2-benzoylbenzoic acid, phen = 1, 10-phenathroline） was used as an electroluminescent material for the first time. The Tb complex was blended with poly（N-vinylcarbazole） （PVK） in different weight ratios and spinn to coated into films （noted as PVK ：Tb films）. The photoluminescence （PL） properties of films were investigated and the optimum weight ratio between PVK and Tb（o-BBA）3（phen） was found to be 3：1. Monolayer devices with the structure ITO/PVK： Tb/AI were fabricated and emitted green light, which was characteristic of Tb^3＋ emission. The results show that mecha- nisms for PL and EL are different. The PL is considered to be caused because of energy transfer and direct excitation to the Tb（o-BBA）3（phen） molecule, while EL is mainly on charging trapping.     

Synthesis and Fluorescence Property of Eu^3 ＋ , Tb^3＋ Perchlorate Complexes with Diphenyl Sulfoxide and 1,10-Phenanthroline

Eu3 ,Tb3 canemitfluorescenceinconjugatedsystemcontainingorganicligand[1,2 ] ,forexample ,1 ,1 0 phenanthroline ,becauseithasbettercoordina tionabilityandbiggerconjugationsystem ,soitcantransmitenergyeffectivelytoEu3 ,Tb3 ,leadingtofluorescenceemission ,andthestabilityisveryhigh ,butsolubilityisverypoor .Inaddition ,diphenylsul foxidehasbettercoordinationabilityandbiggerconju gationsystem ,too .Soitcanalsotransmitenergyef fectivelytoEu3 ,Tb3 ,resutlinginfluorescencee mission ,andsolubi…     

Fluorescence enhancement of Tb（Ⅲ） complex with a new β-diketone ligand by 1,10-phenanthroline

A novel β-diketone, 1-(3,4,5-trisbenzyloxy)benzoyl-5-benzoyl acetylacetone (TBAA), and its corresponding binary Tb(III) complex Tb(TBAA)₃·2H₂O and ternary complex Tb(TBAA)₃Phen with 1,10-phenanthroline (Phen) were prepared. The ligand was characterized based on elemental analysis, FT-IR, and ¹H NMR. The complexes were characterized with elemental analysis, FT-IR and thermogravimetry and derivative thermogravimetry (TG-DTG). Photoluminescence measurements indicated that the energy absorbed by the organic ligand was efficiently transferred to the central Tb³⁺ ions, and the complex showed intense and characteristic emissions due to the ⁵D₄→ ⁷F_J transitions of the central Tb³⁺ ions. Both complexes showed longer fluorescence lifetimes. After the introduction of the second ligand Phen group, the relative emission intensities and fluorescence lifetimes of the ternary complex Tb(TBAA)₃Phen enhanced more obviously than that of the binary complex Tb(TBAA)₃·2H₂O. This indicated that the presence of the ligand TBAA and the second ligand Phen could sensitize fluorescence intensities of Tb(III) ions, and the introduction of Phen group resulted in the enhancement of the fluorescence properties of the Tb(III) ternary rare earth complex.     

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.     

铽在硫氧化镧基质中的光致发光

采用高温固相反应法制备了La2O2S∶Tb3+、La2O2S∶Tb3+,RE3+(RE=Dy,Gd,Ce,Sm)荧光粉样品并进行了相关表征。结果表明,合成样品的晶体结构与La2O2S相同,为六方晶系;荧光粉颗粒的形貌多为长方形片状;发射光谱由494 nm、545 nm、587 nm、622 nm的一系列锐发射峰组成。研究发现Tb3+的掺杂浓度对样品主发射峰545 nm的发光强度影响很大,且在摩尔分数x(Tb3+)=0.02时达到最强。稀土离子Dy3+、Gd3+对La2O2S∶Tb3+荧光粉的发光有明显的敏化作用。     

Luminescence of Terbium Chelates with Substituted Pyridine-2, 6-Dicarboxylic Acid Derivatives by Synergistic Effect of EDTA

Luminescence of Terbium Chelates with Substituted Pyridine-2, 6-Dicarboxylic Acid Derivatives by Synergistic Effect of EDTA     

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.     

Reduction of Tb~(4+) ions in luminescent Y_2O_3:Tb nanorods prepared by microwave hydrothermal method

Terbium doped yttrium oxide was prepared with the microwave hydrothermal method. The Y_2O_3:Tb nanomaterial crystallized as needle-like grains. Bright luminescence in the green region was observed. Significant luminescence intensity increase was obtained after thermal treatment. Reduction of terbium ions was observed after heating in the air atmosphere. Tb~(4+) ions were found to be stabilized by crystal impurities. Hydroxyl species were found to have impact on vacancies elimination. The terbium ions were used as optical and magnetic indicator of the material properties.     

Synthesis and Fluorescence Properties of Europium,Terbium Doped Zn^2＋, Cd^2＋, and Cr^3＋ Complexes

Europium and terbium complexes with strong fluorescence intensity and long fluorescence lifetime were prepared. By replacing half of the europium or terbium ion with M （M = Zn^2＋, Cd^2＋, and Cr^3＋） using the doped method, and then incorporating it with 18-crown-6 ether and terephthalic acid, six heteronuclear samples EuZnLL＇Cl3·3H2O（1）, EuCdLL2＇Cl3·5H2O（2）, EuCrLL＇Cl4· 4H2O（3）, TbZnLL＇Cl3·4H2O（4）, TbCdLL＇2Cl3·4H2O（5）, and TbCrLL＇2Cl4 ·4H2O（6） （L = terephthalic acid, L＇= 18-Crown-6 ether） were obtained. The elemental analysis, molar conductivities, rare earth complexometry, Fourier Transform Infrared Spectroscopy （FT-IR）, ultraviolet （UV）, TGA, fluorescence intensity, and fluorescence lifetime of the samples were measured. The results showed that there were good luminescence properties for heteronuclear complexes （1）, （2）, （4）, and （5）, which were even stronger than those of the homonuclear complexes Eu2LL＇2Cl4·4H2O and Tb2LL＇2Cl4 ·4H2O, but the luminescence properties of EuCrLL＇Cl4·4H2O, TbCrLL＇Cl4·4H2O were very weak. A possible luminescence mechanism was suggested by the organic-inorganic doped mechanism and the law of intramolecular energy transfer.