铕-铽-钆-六氟乙酰丙酮三元配合物的合成与温敏发光性质

合成了铕-铽-钆-六氟乙酰丙酮(HFA)三元配合物Eu0.4Tb0.4Gd0.2(HFA)3(TPPO)2(TPPO: 三苯基氧化磷), 其组成和结构经元素分析和红外吸收光谱确认; 研究了三元配合物的发光性能, 以及铽、钆离子对铕离子发光性能的影响. 结果表明, 配合物中存在着声子支助的Tb3+→Eu3+的能量转移, 增强了Eu3+离子的室温特征荧光发射, 且样品的发光颜色随温度的改变而变化, 具有温敏特性.     

邻苯二甲酸铽配合物与铕离子间能量传递

本文应用红外光谱、紫外吸收光谱、稳态和时间分辨荧光光谱研究了邻苯二甲酸铽及邻甲基苯甲酸铽配合物的发光性能,配位体结构以及铕离子对配合物发光的猝灭方式,并探讨了溶剂、pH值对发光强度和寿命的影响。     

双核双配体稀土配合物Tb1-xEux(TTA)3Phen的合成及光学性能研究

合成了系列铕铽双核稀土有机稀土配合物Tb1-xEux（TTA）3Phen，通过差热．热重分析、XRD、红外光谱、紫外光谱和荧光光谱等测试手段研究了配合物的组成、结构和发光性质。由紫外可见光谱可以看出，稀土有机配合物的吸收峰主要来自有机配体HTrA和1，10-Phen；差热-热重分析证明，稀土有机配合物热稳定性较好。荧光光谱和电致发光表明，铽对铕配合物的发光有协同作用。在该系列配合物中，不仅有机配体可以将吸收的能量传递给发光的铕离子使其发光，而且铽离子也可将其吸收的能量通过分子内能量传递给铕离子，增强铕的发光强度。同时就双核稀土有机配合物光致发光和电致发光的特性及掺杂体系的能量传递过程进行了讨论。     

吡唑啉酮类稀土配合物的发光性质研究

合成了一系列吡唑啉酮类稀土铽、铕、钐、钆、镝的配合物, 并采用元素分析、红外光谱和紫外-可见光谱对其进行了表征, 解析了铕配合物的晶体结构. 测定了配体的三重态能级, 研究了这4种配合物的发光性质. 并通过研究配体到稀土离子的能量传递过程, 合理地解释了这些稀土配合物发光性质的差异.     

高氯酸铕、铽-二苯亚砜-1，10菲咯啉配合物的合成及荧光性质研究

同时合成了高氯酸铕、铽.二苯亚砜-1,10菲咯啉三元配合物和高氯酸铕、铽-1,10菲咯啉二元配合物。以配合物进行了元素分析,摩尔电导。确定了配合物的组成分别为:[RE(DPSO)](phen)3(ClO4)2)ClO4·nH2O(n=1,3,DPSO为二苯亚砜,phen为1,10菲咯啉)和RE(phen)4(ClO4)3。红外光谱研究表明:DP-SO以氧原子与稀土离子配位;phen以氮原子与稀土离子配位;三元配合物中ClO4-中两个与稀土离子配位,二元配合物中三个ClO4-均与稀土离子配位。对比研究了两类配合物的发光性能,溶解性能及稳定性能。研究结果表明:第二配体DPSO的加入,大大改善了配合物的发光性能,可分别使铕、铽的发光强度提高2和8倍。同时大大改善了配合物的溶解性能及稳定性能。     

稀土苯二甲酸配合物的发光性能和分子内能量传递(英文)

合成和表征了一系列稀土（钆，铕，铽）的邻（间）苯二甲酸配合物．通过测定了苯二甲酸配体的钆配合物的低温磷光光谱确定其相应苯二甲酸配体的最低三重态能级．同时详细讨论了配合物的发光性能，能级匹配和分子内能量传递机制．     

影响稀土配合物电致发光性能的几个重要因素

在综述稀土铕和铽配合物电致发光研究进展的基础上, 重点围绕稀土材料本身, 探讨了影响稀土配合物电致发光性能的一些主要问题, 指出一个优异的稀土电致发光材料应兼具有良好的光致发光效率、热稳定性和成膜性以及载流子传输性能.     

稀土配合物发光中的能量传递研究

就稀土发光的能量传递开展了3个方面的初步研究。首先,研究了稀土镧和铕掺杂后共发光的现象和机制;其次是研究了稀土铽配合物作为能量传递桥可以将能量从导电高分子聚乙烯咔唑（PVK）有效地传递给铕配合物;第三,发现通过物理掺杂的方法可以改变稀土铕配合物的激发光谱的形状,使其向着长波长方向移动,这样可以使铕配合物的激发光谱和PVK的发射光谱发生更大的重叠,从而增强它们之间的能量传递效率。     

铕(Ⅲ)、铽(Ⅲ) β-二酮配合物的制备及表征

醋酸铕、醋酸铽分别与乙酰丙酮在60°C水浴下加热回流,生成两种稀土β-二酮配合物,即乙酰丙酮铕(Eu(acac)3?3H2O)和乙酰丙酮铽(Tb(acac)3?3H2O),在紫外灯下观察配合物发光现象,乙酰丙酮铕在紫外灯下显暗红色,乙酰丙酮铽在紫外灯下显亮绿色。红外分析结果与理论相吻合,荧光分析表明它们是较好的荧光材料,热分析结果说明它们的热稳定性相对较高。     

铽苯二甲酸同多核和异多核配合物的发光性能

铽苯二甲酸同多核和异多核配合物的发光性能阎冰张洪杰＊王淑彬倪嘉缵（中国科学院长春应用化学研究所稀土化学与物理开放实验室长春１３００２２）关键词铕，铽，镧，钆，钇，苯二甲酸，配合物，合成，发光性能１９９７－０６－２６收稿，１９９７－０８－２５修回国家自...     

Comprehensive study of the luminescent properties and lifetimes of Eu(3+) and Tb(3+) chelated with various ligands in aqueous solutions: influence of the synergic agent,the surfactant and the energy level of the ligand triplet

The formation and the properties of luminescent complexes of europium and terbium with a variety of organic ligands have been investigated in aqueous solutions. The ligands used include model compounds such as thenoyltrifluoroacetone and pyridine-2,6-dicarboxylic acid and organic analytes of biological or pharmaceutical interest. It is shown that the formation and the luminescent properties of these complexes depend at first on several parameters including the pH and the buffer, the synergic agent and the surfactant. In neutral solutions, trioctylphosphine oxide in the presence of Triton X-100 may act as a co-ligand to promote complex formation and protect the complex from radiationless deactivation processes. Working in slightly alkaline solutions in the presence of EDTA and hexadecyltrimethylammonium chloride may induce the deprotonation of a second coordinating group and favour the formation of a new complex with stronger luminescent properties. In both cases, the luminescence lifetimes are then ultimately related to the energy gap between the ligand triplet and the resonance level of the ion and to the number of water molecules coordinated to the lanthanide ion.     

Luminescent properties of europium(III) and terbium(III) complexes with para- and ortho-ethoxybenzoic acids

The luminescent properties of europium(III) and terbium(III) complexes with para- and ortho-ethoxybenzoic acids are studied. The excitation energies of the triplet states of ligands are determined, a hypothesis is made about the efficient luminescence of europium(III) and terbium(III) complexes, the geometry of the coordination polyhedron of a europium complex is established, and the luminescence quantum yields of the complexes in solution are determined.     

Luminescent nanoparticles prepared by encapsulating lanthanide chelates to silica sphere

The luminescent nanoparticles were prepared by encapsulating the [LnL₄]^? (Ln = Eu, Tb; L = BTFA, HFAA, TTFA, TFAA) complexes anion into the silicon framework. We firstly synthesized a series of novel siloxy-bearing lanthanide complex precursor, and then encapsulated them into the silica sphere by a modified Stöber process. As a result, four europium and two terbium tetrakis β-diketonate complexes functionalized silica sphere nanoparticles were obtained and characterized in detail using Fourier transform infrared spectra, X-ray diffraction, scanning electronic microscope, thermogravimetric analysis, luminescence excitation and emission spectroscopy, luminescence lifetime measurements, and diffuse reflectance UV–Vis spectroscopy. The result shows that these luminescent nanoparticles maintain the distinctive luminescence character of lanthanide chelate including broad excitation spectra, line-like emission spectra, high quantum efficiency, and long luminescent lifetime, which makes them great potential application in the synthesis of luminescent nanoparticle.     

Surface Modification and Functionalization of Microporous Hybrid Material for Luminescence Sensing

We report here on the preparation of novel luminescent core‐shell material by initial coating with polyelectrolytes and subsequent with a silica shell on the lanthanide complexes loaded zeolite L microcrystals. Lanthanide complexes loaded zeolite L was prepared by insertion of 2‐thenoyltrifluoroacetone (TTA) into the nanochannels of zeolite crystals by gas diffusion of TTA to Eu³⁺ exchanged zeolite L, coating a silica shell on the lanthanide complexes loaded zeolite L resulted to the novel luminescent core‐shell material. The luminescent core‐shell material was further functionalized with silylated terbium(III) complex and the obtained material was used as the luminescence sensing of dipicolinic acid (DPA), which is a major constituent of many pathogenic spore‐forming bacteria.     

近红外发光稀土配合物及杂化材料研究进展

稀土因其特殊的物理和化学性质,在信息技术、能源技术、生物技术等高科技领域及国防建设等方面都起着非常重要的作用,中国作为稀土大国,十分重视对稀土材料的研究和开发。稀土离子近红外发光(750～1700 nm)在激光和光纤通讯、医学诊断、免疫分析等热门领域的潜在应用,受到了科研人员的极大关注。稀土离子本身发光极弱,通过分子内传能有机配体可以敏化稀土离子发光,但稀土配合物常受外界干扰,其稳定性较差,若将其与凝胶、介孔材料、离子液体等无机基质复合,得到具有良好光、热稳定性和化学稳定性的有机/无机杂化材料。总结了近些年来近红外发光稀土配合物及近红外发光稀土杂化材料的研究进展,并对其发展前景进行了展望。     

Recent advances in the sensitized luminescence of organic europium complexes

In this paper, recent advances in the synthesis, mechanism of sensitized emission, and luminescent properties of organic lanthanide complexes are reviewed. Stress is put on the progress in the development of organic europium complexes and their nanoparticles with excellent visible-light-sensitized and two-photon-sensitized Eu^III luminescence properties. These are of increasing importance because bioanalysis or bioimaging techniques based on such labeled materials will combine the advantages of high sensitivity, high signal-to-noise ratio, deep penetration, and low photodamage to biological samples. In addition, the application of long-wavelength-sensitized luminescence of organic lanthanide complexes and their nanoparticles in bioimaging is discussed.     

Luminescence studies on europium-strontium phthalate system

New lanthanide luminescence materials were prepared. The main component lanthanide chelates generally need a relatively high content of rare earth. Inorganic luminescence materials only need low rare earth concentration using doped method. Similarly, lanthanide chelates can be added to complex matrix by doped method. In this way, low rare earth concentration emission was successful in the lanthanide chelates system as well. The influence of europium ion concentration on luminescence intensities was discussed. When the europium ion weight in the complex is only about 0.6%, the sample exhibits good luminescence properties. The fluorescence, Fourier transform infrared spectra, micro-Raman and electron spin resonance spectra of the samples were measured. And a possible luminescence mechanism was suggested by the inorganic doped mechanism and the luminescence of lanthanide complexes together.     

A long-lived luminescence and EPR bimodal lanthanide-based probe for free radicals

We developed a novel spin-labeled terbium complex Tb(3+)/cs124-DTPA-TEMPO (1) by covalently labeling a nitroxide radical on the terbium complex for monitoring free radicals of various areas. This lanthanide complex probe shows a high EPR signal which resulted from the nitroxide radical moiety, and is weakly luminescent which resulted from the intramolecular quenching effect of the nitroxide radical on sensitised terbium luminescence. The intensity of both the EPR and luminescence can be modulated by eliminating the paramagnetism of the nitroxide radical through recognition of a carbon-centered radical analyte and thus gives a quantification of the analyte. We have preliminarily applied this probe in the luminescent detection of model carbon-centered radicals and hydroxyl radicals (·OH). This probe is water-soluble and contains lanthanide-luminescence properties, favorable for the time-resolved luminescence technique. The investigation of the intramolecular quenching process has showed that the labeled nitroxide radical quenches multiple excited states of the terbium complex, resulting in highly efficient quenching of terbium luminescence. This probe is the first example of intramolecular modulation of lanthanide luminescence by a nitroxide radical.     

The luminescent properties of divalent europium complexes of crown ethers and cryptands

The luminescent properties of divalent europium complexes with crown ether, azacrown ether, N-pivot-azacrown ether, and cryptand in methanol or water have been systematically investigated under UV irradiation. These divalent europium complexes show greatly enhanced emission from 417 nm to 488 nm in the visible blue region in comparison with that of the methanol solution of EuCl₂. The aqueous solution of EuCl₂ is non-luminescent. This obvious distinction in luminescent properties between the macrocyclic ligand-coordinated divalent europium and uncoordinated divalent europium is attributed to the “insulation effect” of Eu²⁺ ion from the solvent molecules of CH₃OH and H₂O by the macrocyclic crown ether or cryptand encapsulation to divalent europium. Moreover, these macrocyclic ligands provide an additional restriction to the electronic charge expansion of the excited Eu²⁺. This also contributes to the enhancement of the Eu²⁺ luminescence. Among all the investigated macrocyclic ligands, 15-crown-5 (15C5) affords the largest enhancement to the Eu²⁺ emission. The intensity of the Eu²⁺–15C5 complex is 690 times that of the EuCl₂ methanol solution with the same Eu²⁺ concentration. This special emission enhancement effect is related to the particular complex composition of 1:3 (Eu²⁺:15C5) and corresponding configuration of Eu²⁺–15C5 complex in methanol. Concerning the mechanism, the luminescence enhancement of divalent europium by complexation with these macrocyclic crown ether or cryptand ligands is found to be initiated from the decrease in non-radiative rate constant rather than from the increase in radiative one.

The divalent europium complexes of methacrylate polymeric polyether derivatives such as 15C5-, 18-crown-6- (18C6), and cryptand [2.2.1]- or [2.2.2]-containing polymer and copolymer have also been prepared. Their luminescent properties in solid state have been studied to aim for practical application. As a similar situation to the simple polyether complexes, the divalent europium complex with 15C5-containing polymer or copolymer shows the largest luminescent enhancement effect. Its emission intensity reaches about 20% that of the commercial inorganic luminescence product CaWO₄:Pb (NBS 1026). In addition, the doping effect of several divalent ions, namely Mg, Sr, Ba and Zn in polymeric complexes, has also been investigated according to the luminescence concentration quenching mechanism in solid state luminescence materials. The emission intensity of 15C5-containing polymer europium(II) complex is raised to twice stronger by doping of Zn²⁺ ion.