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 Tb0.5 RE0.5(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.

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.

Thermal stability and luminescence properties of 1,10-phenanthroline-tris (m-methylbenzoate) europium (or terbium) complexes in SiO_2 gel

Silica gel luminophors containing 1, 10-phenanthroline-tris(M-Methylbenzoate) europium (or terbium) com- plexes were prepared bysol-gel method. The thermal decomposition, excitation and emissionspectra for the gel phos- phors were measured and compared with thatof solid complex powders. The thermal stability of the complexes wasen- hanced in SiO_2 host matrix and the luminescence intensityremained unchanged.

In-Situ Composition and Luminescence of Europium and Terbium Coordination Polymers/PEMA Hybrid Thick Films

Europium and terbium coordination polymers of pyridine-3-carboxylic acid were in-situ composed with ethyt methacrylate （ EMA ）. With the polymerization of EMA monomer and the formation of europium and terbium coordination polymers of pyridiae- 3-carboxylic acid, the transparent hybrid thick fihns composed of [ Eu（ NIC ）3 ]n （ [ Tb（ NIC）3 ]n ） and poly ethyl mettuwrylate （ PEMA ） have been prepared. The luminescence properties and energy transfer of these polymeric composites were studied with absorption spectra, fluorescent excitation trod emission spectra in detail. All the hybrid thick films composed of terbium coordination polymer show the characteristic strong green emission of terbium ions, which implies the same energy transfer mechanism as the pure complex and the hybrid composite film is a suitable sabstrate for the luminescence of terbium ions. In the range of camposing concentration of luminescent species （0.01,0.025,0.05,0.1 mmol /15 mL EMA ）, emission intensities increase with the increasing of corresponding composing concentration and the concentration quenching effect does not take place.

Synthesis of Tenoltrifluoroacetone Composite Doped with Terbium, Dysprosium and Europium Encapsulated in Silica Oxide Matrix

The synthesis of the thenoyltrifluoroacetone compound doped with terbium, dysprosium and europium encapsulated in a silica matrix (TTA:Tb:Dy:Eu@SiO2) were performed by the sol-gel method. The precursors to obtain the vitreous phase (SiO2) were: Tetraethylorthosilicate (TEOS, C8H2O4Si, 98%, Aldrich), and ethyl alcohol (CH3CH2OH, 99.5%, Meyer), distilled water and 0.05 ml of hydrochloric acid (HCl, Meyer). The sample with molar ratio 20:80 TTA:Tb:Dy:Eu@SiO2 has the best emission intensity. Thermogravimetric analysis (TGA) shown that silica encapsulated samples decompose at lower temperatures than pure TTA:Tb:Dy:Eu luminescent material. Fourier Transform Infrared (IR-TF) shown the characteristic Si-O-Si bands that are presented at a wavelength of 1049, 853 and 440 cm-1 confirming that the luminescent material is encapsulated in a silica matrix, finally X-ray diffraction (XRD) shown that TTA:Tb:Dy:Eu@SiO2 composite is amorphous.

STUDIES ON FLUORESCENCE SPECTRA OF SAMARIUM EUROPIUM TERBIUM AND DYSPROSIUM WITH BENZOYL UREA DERIVATIVES AND PHENANTHROLINE

Rare earth chelates of benzoyl urea derivatives were prepared in ethanol and fluorescence spectra of these chelates were studied in detail. A composition of [RE(BU)_3Phen] (NO_3)_3 was obtained. Correlation between chemical properties of ligands, chelates and spectroscopy was discussed. Intramolecular energy transfer in rare earth chelates was explained.

邻苯二甲酸-邻菲罗啉-铕-铽络合体系的荧光性能研究

波长为３６５ｎｍ的紫外光激发下均可发出特征荧光的邻苯二甲酸－邻菲罗啉－铕和铽固体络合物以机械研磨和化学作用两种方式进行混合，研究了这两系列混合络合物的荧光光谱和红外光谱。结果表明，由于铕、铽之间存在相互影响，其荧光强度变化较大，而荧光发射峰位基本不变。经化学混合后铽对铕的荧光强度有极强的敏化作用，铕对铽具有很强的猝灭作用。

室温固相法合成苯甲酸铕与苯甲酸铽荧光粉

以稀土氯化物、苯甲酸、六次甲基四胺为原料,采用固相反应法合成苯甲酸铕与苯甲酸铽配合物。TG-DTA数据显示,六次甲基四胺盐在200℃左右发生热分解;FT-IR、PL测试结果表明,加入六次甲基四胺后,苯甲酸转化成羧酸盐,与稀土离子形成稳定的配合物,合成配合物具有理想的光致荧光性能。

萘啶酮酸体系荧光法测定铕、铽、镝

本文研究了萘啶酮酸（NA）体系荧光法同时测定铕、铽、镝的最佳条件。在pH值75、3．0×10-4mol／LNA、激发波长342nm的条件下，可分别在612、546、576nm处测定铕、铽、镝，检测限可分别达到1．3、1．0、4．4μg／L。应用本法同时测定了混合稀土试样中铕、铽、镝，取得较满意的结果。

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...

间甲基和邻氯苯甲酸稀土配合物发光性能的研究

本文研究了间甲基苯甲酸稀土配合物ＲＥＬ３（ＲＥ＝Ｅｕ，Ｔｂ；ＨＬ＝ｍ－ＣＨ２Ｃ６Ｈ４ＣＯ２Ｈ）和邻氯苯甲酸稀土配合物ＲＥＬ３·Ｈ２Ｏ（ＲＥ＝ＥＵ·Ｔｂ；ＨＬ＝ＣｌＣ６Ｈ４ＣＯ２Ｈ）的荧光性能，测量了配合物的激发和荧光光谱及其寿命，讨论了晶体结构对能级匹配、能量传递等光谱性质的影响．

稀土离子共掺杂的钼酸钙发光材料的合成与光谱性质

采用了化学共沉淀法合成了一系列的镨、铽共掺杂的钼酸钙发光材料,研究了单掺Pr^(3+)和Tb^(3+)以及CaMoO4∶0.03Pr^(3+),yTb^(3+)共掺杂的浓度、温度对材料发光性能的影响。采用X射线衍射仪(XRD)和荧光光谱对样品进行了晶格结构、荧光性质表征。XRD分析表明:样品的主衍射峰与标准卡片(JCPDS 29-0351的衍射峰数据一致,说明少量Pr^(3+)掺杂没有改变基质晶格结构。荧光光谱分析表明,样品在275nm紫外光激发下,发射光谱主要包括多个发射峰,波长为488,560,621和652nm,分别对应于镨离子的~3P_0-~3H_4,~3P_0-~3H_5,~1D_2-~3H_4和~3P_0-~3F_2的跃迁,在掺杂量为3%时,样品特征发射峰最强,CaMoO4∶0.03Pr^(3+)和CaMoO4∶0.05Tb^(3+)的最佳煅烧温度分别为800和600℃。随着Pr^(3+)和Tb^(3+)掺入量的增加,CaMoO4∶Pr^(3+)发光材料的特征发射光谱和激发光谱的特征峰强度逐渐减小,而CaMoO4∶Tb^(3+)材料发光先减小后增大,存在着浓度猝灭效应。此外,在CaMoO4∶0.03Pr^(3+),yTb^(3+)发光体系中,Tb^(3+)的共掺杂可显著增强镨离子的特征发射峰,这是由于存在Tb^(3+)→Pr^(3+)的有效的能量传递。

(La_(1-x)RE_x)_(2/3)Sr_(1/3)MnO_3 (RE=Y, Sm, Eu, Tb; x=0.1～0.5)的晶体结构及磁性质研究

采用空气中固相反应烧结法制备了一系列钙钛矿结构的(La1-xREx)2/3Sr1/3MnO3(RE=Y,Sm,Eu,Tb;x=0.1～0.5)稀土锰氧化物多晶样品。X射线衍射(XRD)分析表明掺杂RE部分替代La以后,样品的晶体结构为正交结构,空间群为Pbnm。在室温(300K)和液氮温度(77K)下分别测试了样品的磁性质,发现磁性质的改变与RE的掺入量以及RE的离子半径有关。在掺Tb的样品中明显存在巨磁电阻效应,磁场为2T,温度为300和77K分别测得(La0.6Tb0.4)2/3Sr1/3MnO3和(La0.7Tb0.3)2/3Sr1/3MnO3的磁电阻(MR)为80%和85%。随着Tb掺杂量的增加,在不同的磁场下,样品电阻 温度关系曲线的峰均向高温方向移动。

铕、铽依诺沙星配合物的合成和光谱特性

合成了Eu3+、T b3+与依诺沙星配合物,并用元素分析法和ICP-AES法确定了配合物的组成为RE(enx)3C l3.8H2O。红外光谱表明,依诺沙星配体以羧酸根同中心离子发生螯合。紫外光谱表明,配合物的紫外吸收波长较配体稍有红移,且强度明显增强。荧光光谱表明,Eu3+配合物在592nm和612nm处出现Eu3+的特征荧光峰,分别对应5D0-7F1和5D0-7F2的能级跃迁。T b3+配合物在490nm和545nm出现T b3+的特征发射峰,且545nm处发射峰强度最大,二者分别对应5D4-7F6和5D4—7F5跃迁。

铕、铽-2-噻吩甲酸-2,2′-联吡啶配合物的合成、表征及荧光性质研究

合成了铕、铽-2-噻吩甲酸的二元配合物和铕、铽-2-噻吩甲酸-2,2′-联吡啶的三元配合物,并对它们进行了元素分析、稀土络合滴定、摩尔电导测定,确定了配合物组成分别为REL3.2H2O及REL3 L′.C2H5OH(RE=Eu,Tb;L=2-噻吩甲酸、L′=2,2′-联吡啶),测定了配体及配合物的IR谱、1H NMR谱及荧光光谱。IR谱和1H NMR谱测定表明,配体2-噻吩甲酸羧基氧、配体邻菲咯啉2个氮原子与稀土离子配位。荧光光谱实验表明,高氯酸铕和高氯酸铽分别与2,2′-联吡啶和2-噻吩甲酸反应形成的三元配合物的荧光明显强于二元配合物。

新型稀土芳香羧酸类配合物的合成及其光致和电致发光性质

合成了新型可溶性稀土芳香羧酸类配合物,测定了有机配体的三重态能级,并考察了其光致发光相对强度、荧光寿命,发现该系列稀土配合物具有很高的光致发光效率。利用其优良的溶解性,采用高聚物掺杂、旋涂技术将其制成薄膜应用于电致发光研究中,成功地制备出具有高色纯度的稀土有机电致发光器件。对于ITO/PVK/PVK∶Tb(AS)3Phen∶PBD/PBD/Al电致发光器件,其最大亮度为32cd·m-2。

SrBPO_5中铕和铽的发光

利用Ｅｕ３＋和Ｔｂ３＋的电子组态具有共轭性的原理，在空气中合成了ＳｒＢＰＯ５：Ｅｕ，Ｔｂ荧光体系，研究了其光谱特征，发现Ｅｕ３＋和Ｔｂ３＋和Ｅｕ２＋共存于该体系中，且Ｅｕ２＋的发光强度随Ｔｂ３＋离子浓度的增大而增强．

2-噻吩乙酸邻菲口罗啉铕、铽配合物的合成表征及荧光性能研究

合成了以Eu3+,Tb3+及Eu3+,Tb3+掺杂RE3+(La3+,Gd3+,Y3+)为中心,以2-噻吩乙酸和1,10-邻菲口罗啉为配体的两个系列8种同核与掺杂稀土固体配合物。对其进行了稀土及C、H和N元素分析、摩尔电导、热谱、红外光谱、核磁共振氢谱的测定及荧光性能研究。确定了配合物的组成为REL3L′和RE0.5Ln0.5L3L′(RE=Eu,Tb;Ln=La,Gd,Y;L=2-噻吩乙酸;L′=1,10-邻菲口罗啉,在常温下测定了它们的固态粉末荧光光谱,发现掺杂离子(La3+,Gd3+,Y3+)使稀土Eu3+离子发光明显增强,讨论了掺杂稀土离子对铕、铽配合物的发光影响。

克量级铀中微量铕和铽的放化分离方法研究

为提高中子诱发铀裂变时低产额裂变产物156 Eu和161 Tb产额测量的精度,需获得放化纯的156 Eu和161 Tb样品。本工作建立了氢氧化物共沉淀法除铝、氟化钙共沉淀法除铀、TRPO萃取法提取稀土元素、阳离子交换色谱法从混合稀土元素中分离Eu和Tb的流程,可用于大量铀、铝和裂变产物中微量Eu和Tb的分离。在待分离样品中含2 g铀、0.65 g铝和裂变产物的条件下,该流程对Eu、Tb的化学回收率均大于80%,对U、239 Np、95 Zr、103 Ru、131 I、132 Te、140 Ba、140 La、141 Ce、147 Nd等主要干扰物质的去污因子达到106。该方法可满足中子诱发铀裂变时156 Eu和161 Tb产额精确测量的要求。

均苯三甲酸Eu-Tb配合物的合成及荧光性质研究

以H3BTC为配体,用水热法合成了均苯三甲酸Eu-Tb系列发光配合物Eu1-xTbxBTC.nH2O(H3BTC=1,3,5-均苯三甲酸,x=0,0.1,0.3,0.5,0.7,0.9,1.0;n=0,0.5),通过化学分析及元素分析确定了配合物的组成,用红外光谱对其进行了表征;研究了配合物的激发光谱和发射光谱,并就其荧光强度与两种稀土离子含量之间的关系进行了讨论。结果表明:(1)该系列配合物(除纯均苯三甲酸Tb外)均发出Eu离子的特征荧光,而荧光强度随着Eu和Tb离子的不同发生了明显变化,发射峰位置基本不变;(2)系列配合物中Tb对Eu的荧光强度有敏化作用,Eu对Tb的荧光强度有猝灭作用;同时Eu离子的5D0→7F1和5D0→7F2跃迁发射强度较强,且均劈裂为两个峰(587,593 nm)及(611.2,618 nm),这是由于Eu离子所处的配位环境不同所引起的。