Eu3+或Tb3+掺杂的KY2F7纳米球的制备与表征

利用简单的室温液相反应制备了KY₂F₇及镧系离子掺杂的KY₂F₇∶Eu³⁺和KY₂F₇∶Tb³⁺的纳米球，并利用XRD，TEM，SEM，XRF和荧光光谱对所制备的材料进行了表征。研究表明Eu³⁺或Tb³⁺离子已成功地掺杂在KY₂F₇纳米球中。掺杂     

Ce3+,Tb3+,Eu3+共掺杂Sr2MgSi2O7体系的白色发光和能量传递机理

通过正交试验,采用高温固相法制备了Sr2-x-y-zMgSi2O7∶xCe3+,yTb3+,zEu3+系列样品.使用X射线衍射仪和荧光光谱仪表征了样品的物相和发光性质,并讨论了Ce3+-Tb3+-Eu3+共掺杂Sr2MgSi2O7体系中的能量传递过程.实验结果表明,在327 nm波长激发下,所合成荧光粉的发射峰主要位于387 nm(蓝紫)、542nm(绿)和611 nm(红)处;分别以387,542和611 nm为监控波长,所得激发光谱显示荧光粉在327 nm处有最好的激发.在327 nm光激发下,系列样品发光进入白光区.最优化的荧光粉为Sr1.91MgSi2O7∶0.01Ce3+,0.05Tb3+,0.03Eu3+,其色坐标为(0.337,0.313),是一种潜在的发光二极管(LED)用白色荧光粉.     

Optical characterization of Eu3+ and Tb3+ ions doped zinc lead borate glasses

This paper reports on the spectral analysis of Eu3+ or Tb3+ ions (0.5 mol%) doped heavy metal oxide (HMO) based zinc lead borate glasses from the measurement of their absorption, emission spectra and also different physical properties. From the XRD, DSC profiles, the glass nature and glass thermal properties have been studied. The measured emission spectrum of Eu3+ glass has revealed five transitions (5D0-->7F0, 7F1, 7F2, 7F3 and 7F4) at 578, 591, 613, 654 and 702 nm, respectively, with lambdaexci=392 nm (7F0-->5L6). In the case of Tb3+:ZLB glass, four emission transitions such as (5D4-->7F6, 7F5, 7F4 and 7F3) that are located at 489, 542, 585 and 622 nm, respectively, have been measured with lambdaexci=374 nm. For all these emission bands decay curves have been plotted to evaluate their lifetimes and the emission processes that arise in the glasses have been explained in terms of energy level schemes.     

钇(Ⅲ)、铽(Ⅲ)、铒(Ⅲ)对氨基苯甲酸配合物共掺杂二氧化硅的光声光谱研究

合成了Tb(p-ABA)₃·H₂O和Ln(p-ABA)₃·H₂O(p-ABA: 对氨基苯甲酸, Ln: Y或Er)配合物共掺杂的SiO₂样品. 荧光光谱测定结果表明, Y(p-ABA)₃·H₂O的引入增强了样品中Tb³⁺离子的特征发光, 而Er(p-ABA)₃·H₂O的引入使Tb³⁺的发光减弱. 光声光谱结果表明, 与Tb³⁺配合物单掺的样品相比, Tb³⁺和Y³⁺配合物共掺样品的光声强度降低; 而Tb³⁺和Er³⁺配合物共掺的样品则情况相反. 实验测定了共掺杂样品的相对量子发光效率和发光寿命, 从无辐射跃迁和辐射跃迁的角度提出共发光效应可能的机制. 结合对室温下陈化干燥样品的分析发现, 只有经适当的热处理过程才能在SiO₂凝胶中形成具有多核结构的稀土配合物.     

Syntheses, structures and properties of seven isomorphous 1D Ln3+complexes Ln(BTA)(HCOO)(H2O)3 (H2BTA = bis(tetrazoly)amine, Ln = Pr, Gd, Eu, Tb, Dy, Er, Yb) and two 3D Ln3+ complexes Ln(HCOO)3 (Ln = Pr, Nd)

Seven isomorphous 1D chain Ln3+ complexes Ln(BTA)(HCOO)(H2O)3 (Ln = Pr (1), Gd (2), Eu (3), Tb (4) Dy (5), Er (6) and Yb (7)), and two formate coordinating and bridging 3D Ln3+ complexes Ln(HCOO)3 (Ln = Pr (8) and Nd (9)) have been synthesized and characterized by single crystal X-ray diffraction analysis. Although the Ln3+ ions in 1-7 have different radius, the trivalent lanthanide ions in 1-7 show the same coordinated environment. The well-defined single crystal structures of 8 and 9 are first samples for formate-bridged Ln3+ metallic complexes. The luminescent properties of solid samples of 2-5 at room temperature and the magnetic property of 2 have been also reported and discussed in this paper.     

Photofunctional Eu3+/Tb3+ hybrids through sulfoxide linkages: coordination bonds construction, characterization and luminescence

New kinds of organic-inorganic hybrid materials consisting of rare earth (Eu(3+), Tb(3+)) complexes covalently bonded to a silica-based network have been obtained by a sol-gel approach. Three novel versatile molecular building blocks containing sulfoxide organic units have been synthesized by methylene modification reaction, which are used as the ligands of rare earth ions and also as siloxane network precursors. The obtained hybrids are characterized by chemical analysis and spectroscopic methods such as FTIR and UV; XRD and SEM. Photoluminescence measurements on the prepared hybrids were performed showing the intra-4f(n) emission in the visible (Eu(3+), Tb(3+)) region and in all the cases being sensitized by the sulfoxide ligands. The emission quantum efficiency and the Judd-Ofelt intensity parameters of Eu(3+) hybrid materials were also investigated in detail.     

Study of lanthanide complexes with salicylic acid by photoacoustic and fluorescence spectroscopy

Solid complexes Ln(Sal)3.H2O (Sal: salicylic acid; Ln: La3+, Nd3+, Eu3+, Tb3+) are synthesized, and their photoacoustic (PA) spectra in the UV-Vis region have been recorded. PA intensities of central lanthanide ions are interpreted in terms of the probability of nonradiative transitions. It is found that PA intensity of the ligand increases in the order of Tb(Sal)3.H2O < La(Sal3).H2O < Eu(Sal)3.H2O < Nd(Sal)3.H2O. Different PA intensities of the ligand are interpreted by comparison with the fluorescence spectra. Ternary complexes Eu(Sal)3Phen and Tb(Sal)3Phen (Phen: 1,10-phenanthroline) are synthesized. Compared with their binary complexes, PA intensity of the ligand Sal decreases for Eu(Sal)3Phen, while the reverse is true for that of Tb(Sal)3Phen. The luminescence of Eu3+ increases remarkably when Phen is introduced, and luminescence of Tb3+ decreases greatly when Phen is added. The intramolecular energy transfer and relaxation processes in the complexes are discussed from two aspects: radiative and nonradiative relaxations.     

A Cl- anion-responsive luminescent Eu3+ complex with a chiral tripod: ligand substituent effects on ternary complex stoichiometry and anion sensing selectivity

A new series of N3,O-mixed donor tripods was prepared for luminescent Eu3+ complexes, in which the soft quinoline nitrogen, tertiary amine nitrogen, and hard amide oxygen donors were cooperatively involved. The mixed donor tripods formed more stable 1 : 1 complexes with Eu(NO3)3, La(NO3)3 and Tb(NO3)3 than the corresponding N4 donor tripods, and their Eu3+ complexes particularly exhibited anion-responsive luminescence properties. NMR, UV, and luminescence spectroscopic characterizations revealed that -CH3 substitution on the tripod skeleton remarkably altered the preferred stoichiometry of the "tripod-Eu3+-anion" ternary complex and gave anion-dependent europium luminescence. Although the disubstituted tripod preferred to form non-luminescent 2 : 1 (tripod : Eu3+) complexes with Eu(NO3)3 and other salts, it formed a luminescent 1 : 1 complex with EuCl3. Thus, this type of tripod offered Cl- anion-selective luminescence enhancement that was easily observed by the naked eye.     

[（n—C4H9）4N][EuxM1—x（TTA）4]（M=La、Sm、Gd、Tb）的光致发光

合成了一类组成为[(n-C4H9)4N][EuxM1-x(TTA)4](M=La、Sm、Gd、Tb）的固体配合物，通过测定其红外光谱，X射线粉末衍射谱和荧光光谱，研究了配合物结构和发光性质随Eu^3 浓度变化的规律。红外光谱和XRD谱的分析结果表明，在体系中没有新化合物生成，而荧光光谱分析结果表明发光强度与Eu^3 浓度不成线性关系，不发光的基质配合物组分对发光有不同大小和不同类型的影响，提出一种可能的发光机制解释这一共发光现象。     

Effect of ligand structure on synergism in Tb3+-aromatic acid complexes: fluorescence lifetime studies

The fluorescence of Tb3+ sensitized by aromatic carboxylic acid ligands (benzoic, monomethylphthalic, monomethylterephthalic, trimesic, terephthalic, isophthalic, phthalic and mellitic acids) and the synergism displayed by these complexes when treated with TOPO/Triton X-100 have been studied by measuring lifetimes of Tb3+ emission. The lifetime of Tb3+ fluorescence was not significantly altered following complex formation with aromatic carboxylic acids, even though a significant enhancement in the Tb3+ fluorescence intensity was observed in every single case. However, when these Tb3+-aromatic acid complexes were treated with TOPO/Triton X-100, the lifetimes of the Tb3+ fluorescence increased markedly, but only with certain acids. Interestingly, even amongst the acids that showed an increase in lifetime with TOPO/Triton X-100, the lifetimes as a function of the pH of the solution was strongly dependent on the structure of the ligand. These differences and the reasons for such behavior are discussed, which shed light on the role of the structure of the ligand on the synergism process.     

Luminescence of Tb3+ and Eu3+ doped amorphous zinc benzoates

The Tb(3+) and Eu(3+) doped amorphous zinc benzoate were prepared. Their infrared absorption, emission and excitation spectra were measured. The luminescence mechanisms of Tb(3+) and Eu(3+) in the amorphous substrate were discussed. The bonding modes of OCO group to Zn(2+) ion have two of symmetric and asymmetric bridging bidentate. The energy of the S(1) pi,pi* excited state of benzene ring can be transferred to Tb(3+) and Eu(3+) ion, and results in characteristic emission from the 5D(4)-->(7)F(j) of Tb(3+) and 5D(0)-->(7)F(j) of Eu(3+), respectively.     

Synthesis and Luminescent Properties of Eu 3+ , Gd 3+ , and Tb 3+ Complexes with Quinoline-4-carboxylic Acids

New complex compounds LnL3·nH2O (n = 5–10) have been synthesized on the basis of Eu3+, Gd3+, and Tb3+ salts and quinoline-4-carboxylic acid derivatives obtained via the Pfitzinger reaction. Composition and structure of the ligands and the resulting complex compounds have been confirmed by NMR and IR spectroscopy, thermogravimetry, and complexometric titration. Europium complex with 1,2,3,4-tetrahydroacridine-9-carboxylic acid has exhibited efficient luminescence.     

Laser spectroscopic studies of Tb3+-doped oxyfluoroborate glass

Tb3+-doped oxyfluoroborate glasses have been prepared for different concentrations of Tb. The absorption, fluorescence and photoacoustic spectra of these have been recorded and studied. It is marked that the fluorescence intensity of different fluorescence transitions decreases with the increase of Tb ion concentration in the glass. This quenching at higher concentration is due to the energy transfer among the excited and nearest neighbor unexcited Tb ions in the glass. The lifetime measurement confirms it, as the lifetime of a particular state was found to decrease with the increase of Tb ion concentration in the glass. The mechanism of the energy transfer process was determined to involve quadrupole quadrupole interaction. We have also studied the energy transfer from Tb3+-->Pr3+ when both the rare earths are doped together in the glass. A decrease in the lifetime of the 5D4 level of Tb3+ with the increase of Pr3+ concentration confirms this.     

Tb3+/Eu3+镧系金属有机框架材料在荧光检测的研究进展

镧系金属有机骨框架（Lanthanide metal organic frameworks,Ln-MOFs）是以镧系离子为中心,与配体有机物组合的多孔材料,具有良好的光学性质,在许多领域有广泛的应用。不同的镧系离子与相应的有机配体结合,可组成不同性能的Ln-MOFs。在众多镧系元素中,Tb3+和Eu3+是良好的发光中心,常被用于组建发光Ln-MOFs。由Tb3+/Eu3+与有机配体形成的Ln-MOFs具有独特的荧光特性、较大stokes位移以及长发光寿命等优点在荧光检测领域具有重要应用。本文综述了基于Tb3+/Eu3+的Ln-MOFs在离子检测、生物标志物检测以及小分子检测领域的研究进展,对Ln-MOFs的发展前景进行了展望。     

Optical studies of Eu3+ doped oxyfluoroborate glass

Rare earth doped oxyfluoroborate glasses have been prepared with different concentration of Eu3+. The UV-Vis/NIR optical absorption, laser induced fluorescence and photoacoustic spectra of Eu3+ in this host have been studied. Different optical parameters such as oscillator strength, Judd-Ofelt intensity parameter, stimulated emission cross-section, transition probability, branching ratio and radiative lifetime, etc. have been calculated. Lifetime of the 5D0 level at various concentrations of Eu3+ have been used to explain the concentration dependent fluorescence quenching. The mechanism of quenching was found to be dipole-dipole. Energy transfer have also been studied from Eu3+ to Pr3+ in sample with 1 mol% (Eu3+) + 1 mol% Pr3+.     

在硅磷酸镧中Ce^3＋离子对Tb^3＋离子的敏化

实验表明在La2O3·0.01SiO2·0.95P2O5基质中Ce^3 对Tb^3 有强的敏化作用。254nm紫外光激发下温度对Tb^3 激活的Ce^3 、Tb^3 共激活试样的发射强度的Ce^3 、Tb^3 共激活的试样Tb^3 的^5D4→^7F6:5:4跃迁的发射强度随湿度的变化。计算了Ce^3 到Tb^3 的能量传递效率。初步探讨了Ce对Tb的能量传递机理。     

Chemical size effect on the magnetic and electrical properties in the (Tb(1-)(x)Eu(x))MnO(3) (0 < or = x < or = 1.0) system

The effect of isovalent chemical substitution of Eu3+ into the Tb3+ sites on the magnetic and electrical properties of (Tb1-xEux)MnO3 (0 相似文献   

Time-resolved long-lived luminescence imaging method employing luminescent lanthanide probes with a new microscopy system

Superior fluorescence imaging methods are needed for detailed studies on biological phenomena, and one approach that permits precise analyses is time-resolved fluorescence measurement, which offers a high signal-to-noise ratio. Herein, we describe a new fluorescence imaging system to visualize biomolecules within living biological samples by means of time-resolved, long-lived luminescence microscopy (TRLLM). In TRLLM, short-lived background fluorescence and scattered light are gated out, allowing the long-lived luminescence to be selectively imaged. Usual time-resolved fluorescence microscopy provides fluorescence images with nanosecond resolution and has been used to image interactions between proteins, protein phosphorylation, the local pH, the refractive index, ion or oxygen concentrations, etc. Luminescent lanthanide complexes (especially europium and terbium trivalent ions (Eu3+ and Tb3+)), in contrast, have long luminescence lifetimes on the order of milliseconds. We have designed and synthesized new luminescent Eu3+ complexes for TRLLM and also developed a new TRLLM system using a conventional fluorescence microscope with an image intensifier unit for gated signal acquisition and a xenon flash lamp as the excitation source. When the newly developed luminescent Eu3+ complexes were applied to living cells, clear fluorescence images were acquired with the TRLLM system, and short-lived fluorescence was completely excluded. By using Eu3+ and Tb3+ luminescent complexes in combination, time-resolved dual-color imaging was also possible. Furthermore, we monitored changes of intracellular ionic zinc (Zn2+) concentration by using a Zn2+-selective luminescent Eu3+ chemosensor, [Eu-7]. This new imaging technique should facilitate investigations of biological functions with fluorescence microscopy, complementing other fluorescence imaging methodologies.     

Group I cation templated formation of luminescent mono- and bis-substituted thionaphthol heterobimetallic complexes of Pr, Nd, Eu and Tb

Metathesis of lanthanide tris di-tert-butyl beta-diketonates ([Ln(thd)3] Ln=Pr, Nd, Eu, Tb) with one or two equivalents of group 1 salts of the sulfur bridged binaphtholate dianion [1,1'-S(2-OC10H4But(2)-3,6)2]2-, [M2L], M=K, Li affords luminescent mono- and bis-ligand substituted complexes ML[LnL(thd)2].L; M=K, Ln=Pr , Nd , Eu and Tb (L=thf, diethyl ether or toluene) and M(thf)2[LnL2(thd)]; M=Li, Ln=Pr , Nd , Eu , Tb . The potassium salt [K2L] affords mono-L substituted complexes most cleanly, while the lithium salt [Li2L] yields the bis-L substituted complexes most cleanly. The L ligands function as antenna for the sensitised lanthanide-centred emission in Eu3+ and Tb3+ complexes. The X-ray single-crystal structures of mono- and bis-L lanthanide complexes of Nd3+ are presented.     

Highly resolved luminescence measurements for traces of 1,3-dibetanato europium(III) and terbium(III) complexes using a microscope laser Raman spectrometer toward the forensic discrimination.

The emission spectra of luminescent trivalent europium (Eu3+) and terbium (Tb3+) complexes were measured using a microscope laser Raman spectrometer with a doubled Nd:YAG laser (532 nm) and an Ar laser (488 nm). Excitation at 532 and 488 nm corresponded to wavelengths of the 7F1 --> 5D1 band of Eu3+ and the 7F6 --> 5D4 band of Tb3+, respectively. The Eu3+ and Tb3+ complexes were discriminated by high-resolution emission spectra more distinctly and sensitively than by fluorescence spectrometry, the usual analytical method.