苯甲酸-铕-铽配合物的荧光光谱研究

合成了苯甲酸－ 铕－ 铽和苯甲酸－ 铕－ 铽－ 镧系列固体配合物,研究了它们的荧光发射光谱。结果表明,Ｔｂ３＋ 对Ｅｕ３＋ 的荧光发射有很强的敏化作用,而Ｅｕ３＋ 对Ｔｂ３＋ 的荧光发射有很强的猝灭作用;但Ｅｕ３＋ 和Ｔｂ３＋ 的荧光发射峰的位置基本上保持不变。     

对苯二甲酸铕锶、铽锶掺杂配合物的红外光谱及荧光光谱研究

采用稀土掺杂的方法合成了铕锶、铽锶的对苯二甲酸(L)配合物,并对系列配合物进行了红外光谱测定和荧光光谱研究。实验结果表明,共掺杂配合物的羧基氧与稀土离子配位。铽锶配合物T b-S r-L和铕锶配合物Eu-S r-L的发光性能较好。在上述配合物中加入荧光惰性离子Y3+形成T b-S r-Y-L和Eu-S r-Y-L配合物可以使对苯二甲酸铕锶、铽锶配合物体系的荧光得到进一步增强,这可能是由于存在有效的分子内传能,使发光稀土离子Eu3+和T b3+受到敏化作用而使荧光增强;而加入Zn2+和M n2+使体系的荧光减弱,铽锶配合物及其掺杂配合物T b-S r-Y-L是较理想的发光配合物。     

铕三元配合物的合成、表征及其光致发光性能

以苯甲酸、邻苯二甲酸、间苯二甲酸、水杨酸、丙烯酸、甲基丙烯酸、α—噻吩基三氟甲酰丙酮为第一配体,二安替比林甲烷,三正辛基氧化膦、2,2’-联吡啶、邻菲咯啉及邻菲咯啉N-氧化物为第二配体,合成了系列铕三元配合物。经元素分析确定了它们的组成;研究了它们的紫外吸收光谱、红外吸收光谱及荧光光谱。紫外光谱的研究表明,配合物的紫外吸收主要表现为配体的吸收,但是吸收峰的位置发生了移动;红外光谱的研究表明,配合物的红外光谱不同于自由配体的红外光谱,在400~500 cm-1出现了吸收峰,这是Eu-O的伸缩振动峰;荧光光谱的研究表明,第二配体的加入可以显著提高配合物的荧光性能。     

对硝基苯甲酸铕与2,2‘—联吡啶配合物的合成及热分解的研究

在乙醇溶液中合成了一种新的铕（Ⅲ）的三元配合物，通过元素分析、红外光谱分析对其进行了表征。采用ＴＧ－ＤＴＧ技术对其热分解过程进行了研究，并用三种非等温积分方程计算了动力学参数。     

掺杂卤代苯甲酸、含氮杂环铕配合物的合成、表征及荧光性能研究

分别以对溴苯甲酸和对碘苯甲酸为第一配体、含氮杂环(TPTZ和phen)为第二配体,以单一稀土Eu3+和Eu3+掺杂Gd3+、y3+为中心合成了12种配合物.对其进行了元素分析、紫外光谱、红外光谱、荧光激发和发射光谱的测定.推测化合物的组成分别为:(1)Eu(P- BrBA)3(TPTZ)·2H2 O; (2) Eu(P - IBA)3 (TPIZ)·2H2O;(3)Eu0.5Gd0.5 (P - BrBA)3 (TPTZ)·2H2O; (4) Eu0.5 Gd0.5(P- IBA)3(TPTZ)· 2H2O; (5) Eu0.5Y0.5(P - BrBA)3(TPTZ)· 2H2O;(6)Eu0.5Y0.5(P-IBA)3(TPTZ) · 2H2O;(7)Eu(P-BrBA)3(phen)· 2C2H5OH;(8)Eu(P- IBA)3(phen)· 2C2 H5 OH; (9) Eu0.5 Gd0.5(P- BrBA)3(phen)·2C2H5OH; (10) Eu0.5Gd0.5(P- IBA)3( phen).2C2H5OH;(11)Eu0.5Y0.5(P- BrBA)3(phen)·2C2H5OH和(12) Eu0.5Y0.5(P- IBA)3 (phen)·2C2H5 OH.卤代苯甲酸的羧基氧和稀土离子配位,TPTZ和phen的氮原子与稀土离子成键;配合物的形成对配体的共轭π-π*跃迁影响不大;几种不同的卤代苯甲酸铕配合物的发光强度有所差别,对溴苯甲酸配合物较强,中性配体TPTZ强于phen;掺钆、钇的铕配合物的荧光强度大于纯铕配合物,表明掺杂配合物并非简单配合物的混合,而是有一定混配配合物形成.     

铽及其掺杂对苯二甲酸冠醚配合物的合成与荧光性能研究

合成了铽及掺荧光惰性镧、钆、钇的铽冠醚对苯二甲酸配合物。通过元素分析、摩尔电导及红外光谱推测出了配合物的组成;实验结果表明,半径大的稀土离子与18冠6的氧原子直接配位,而半径小的稀土离子则通过水分子配位;对苯二甲酸作为桥连配体连接两个稀土冠醚配合物。测定了配合物的荧光激发光谱和发射光谱,表明铽配合物发出较强的荧光。探讨了配合物中的传能过程,结果表明,配体能较好地将吸收的能量传递给T b3+,不发光稀土离子(L a3+、G d3+和Y3+)对发光稀土离子(T b3+)具有很强的敏化作用,比较这三个含有惰性稀土离子的配合物,发现L a3+的敏化作用最强。     

铽-钆-苯甲酸-三苯基氧化膦的合成及荧光光谱研究

本文采用乙醇为溶剂，水浴加热回流的方法，合成了Tb3+-苯甲酸-三苯基氧化膦（TPPO）、Tb3+－Cd3+（Y3+）-苯甲酸-三苯基氧化膦等绿色荧光液膜材料。常温下研究了它们的荧光光谱，发现三元液膜配合物Tb3+-苯甲酸-三苯基氧化膦比二元固体配合物Tb3+-苯甲酸的荧光强度大大增加，如果在三元配合物中掺入Gd3+或Y3+离子，其掺杂配合物比原三元配合物的发光强度增加了4～5倍。得到了发鲜艳绿色荧光的高效液膜发光材料（Tb3+－Gd3+-苯甲酸-三苯基氧化膦）。     

稀土三元配合物的合成、结构表征及荧光性能研究

合成了铈-草酸-丙烯酸三元固体配合物。利用元素分析、红外光谱（FT-IR）、紫外．可见光谱（UV-Vis）、热重分析（TGA）和荧光光谱等手段研究了配合物的结构和性质。结果表明配合物的组成为[Ce（OOC-COO）（CH2=CH-COO）]·3H2O，荧光光谱表明，配合物中的有机配体能够有效地把吸收的能量传递给中心Ce^3＋离子，强烈敏化Ce^3＋发光，且发射谱线很窄，主发射峰为Ce^3＋的5d→^2F7/2跃迁，这对寻找新型稀土配合物发光材料和制备有机电致发光器件具有一定的价值。     

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。     

对硝基苯甲酸铕与2,2′-联吡啶配合物的合成及热分解的研究

在乙醇溶液中合成了一种新的铕(Ⅲ)的三元配合物,通过元素分析、红外光谱分析对其进行了表征.采用 TG-DTG 技术对其热分解过程进行了研究,并用三种非等温积分方程计算了动力学参数.     

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.     

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.     

Synthesis and Properties of Ternary Europium Complexes with Aromatic Carboxylic Acid and ,Nitrogen-Containing Heterocyclic Ligand

Synthesis and Properties of Ternary Europium Complexes with Aromatic Carboxylic Acid and Nitrogen-Containing Heterocyclic Ligand     

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 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-phenanthmline, 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 morn 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 Fluorescence Studies on Complexes of Terbium with Phenylglyoxylic Acid, 2, 2-Dipyridine, 1, 10-Phenanthroline, Triphenyl Phosphine Oxide

Synthesis, Characterization and Fluorescence Studies on Complexes of Terbium with Phenylglyoxylic Acid, 2,2-Dipyridine, 1,10-Phenanthroline, Triphenyl Phosphine Oxide     

Synthesis, Structure and Fluorescence Properties of Tb(Ⅲ) Complex with Isonicotinic Acid and Biphenyl-2,2''-Dicarboxylic Acid

Terbium perchlorate reacted with isonicotinic acid (Hpya) and biphenyl-2,2'-dicarboxylic acid (H2dpa) under hydrothermal condition, a new ternary terbium complex [Tb(pya)(dpa)(H2O)]n (1) was synthesized. The structure of the ternary complex was determined by X-ray single crystal diffraction and characterized by elemental analysis, fluorescence measurement. The fluorescence spectrum shows the title complex emits strong green light. The crystal data for the complex: monoclinic, P21/n space group, a=0.8908(5) nm, b=1.0569(6) nm, c=2.0969(11) nm, β=98.446(8)°, V=1.9528(18) nm3, Z=4, R=0.0241, wR2=0.0534. The center Tb3 ion is eight coordinated. The coordination polyhedron around Tb3 ion can be described as a distorted square antiprism. The complex forms an infinite one-dimensional alternating chain polymer by bridging carboxyl groups of pya and dpa.     

铽芳香羧酸丙烯酰胺三元配合物的合成及发光性能研究

以对甲基苯甲酸、对氨基苯甲酸、磺基水杨酸、大茴香酸、水杨酸为第一配体,丙烯酰胺为活性配体,合成了五种新的铽芳香羧酸丙烯酰胺三元配合物。通过元素分析,EDTA配位滴定分析,热分析,红外、紫外、荧光光谱分析对目标配合物的组成、结构进行了表征,并研究了它们的发光性能。结果表明,五种新的活性铽三元配合物均具有良好的发光性能,各芳香羧酸向铽离子传递光能的能力为:大茴香酸>磺基水杨酸>对氨基苯甲酸>对甲基苯甲酸>水杨酸,将这些含活性配体丙烯酰胺的铽发光配合物引入高分子化合物中可望合成出键合型铽高分子发光材料。