对苯基苯甲酸铕、铽配合物的合成、表征及荧光性能研究

分别合成了以对苯基苯甲酸为配体,铕、铽及掺杂铕、铽为中心的固态配合物。经元素分析、摩尔电导及差热-热重分析,推测其组成分别为:铕配合物:EuL3.3H2O、Eu0.5La0.5L3.3H2O、Eu0.5Y0.5L3.3H2O;铽配合物:TbL3.2H2O、Tb0.5La0.5L3.2H2O、Tb0.5Y0.5L3.3H2O(L=■-■-COO-。红外光谱、紫外光谱及核磁共振氢谱分析表明,对苯基苯甲酸的羧基氧原子与稀土离子配位。配合物的荧光光谱测定表明,铕系列和铽系列配合物都可发出其特征荧光,铕异核稀土配合物的荧光强度与相同配体的铕配合物相比,均有不同程度提高。     

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。     

铕与5-氰基间苯二甲酸配合物的合成及发光性能

在水溶液中合成了铕与5-氰基间苯二甲酸配合物,它在紫外线辐照下能发出明亮的红光.元素分析表明,其组成为EuLCl·3H2O(L = C6H3CN(COO)22-),配合物的紫外吸收主要是配体的吸收;红外吸收光谱表明,配合物中Eu3+与羰基氧双齿螯合配位;荧光光谱表明,配合物具有良好的荧光性能,最佳激发波长为395nm,发射光谱为Eu3+ 的特征光谱,最强发射峰位于616nm,Eu3+处于无反演对称中心格位上,荧光发光机理属于M-M型.     

缩聚活性铕配合物的合成与表征

采用一种新方法制备无水稀土配合物,其中一步法直接合成三氯化铕的绝对无水乙醇溶液。在稀土配合物中引入带胺基的功能配体,使其与三氯化铕反应合成了两种两端含有胺基具有缩聚活性的配合物。以元素分析、红外光谱和紫外光谱对配合物的组成和结构进行表征,并以摩尔电导和荧光光谱对配合物的性质进行研究,结果表明,在DM F中配合物可作为聚合单体应用;粉末状态下,配合物具有高的荧光强度,荧光单色性好。     

铕掺杂配合物的合成及其荧光性质研究

采用稀土掺杂的方法以Zn2+与Eu3+、配体对氯苯甲酸(CBA)、邻菲罗啉(Phen)合成铕掺杂配合物铕-锌-对氯苯甲酸-邻菲罗啉(Eu-Zn-CBA-Phen).经元素分析,推测其组成为:Eu1-xZnx(CBA)3-xPhen*H2O(x=0～0.8).红外光谱分析证实,铕与配体发生配位,而紫外与荧光光谱分析表明,随着Zn2+取代配合物中部分Eu3+,配合物的荧光强度明显增加,当掺杂Zn2+与Eu3+摩尔分数比为2∶3时,荧光强度达到最大值.同时还系统地考察了非稀土金属离子的加入对配合物荧光性能的影响和荧光增强机理.     

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。     

Eu3+-Sm3+稀土配合物的合成与性能表征

合成了Eu3+、Eu3+-Sm3+稀土配合物,采用红外光谱、X-射线衍射对稀土配合物的组成和结构进行了表征,通过热分析表征了配合物的热性能,荧光分析测试了配合物的激发光谱和发射光谱。结果表明,Eu3+、Eu3+-Sm3+稀土配合物Eu3+的特征荧光发射,Sm3+的引入使得Eu3+的发光强度减弱。     

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.     

新型铈苦味酸配合物的合成、表征及其与白蛋白相互作用

合成了一种新的配体2,7-二(二苯胺酰乙氧基)萘及其铈苦味酸盐的配合物,采用1HNMR、红外光谱、元素分析、摩尔电导及热分析对其结构进行了表征,推测配合物的组成为[Ce(pic)3L2]。在pH=7.30的TrisHCl缓冲溶液中采用荧光光谱法分别研究了配合物与HSA、BSA、VOA的作用方式。结果表明,配合物对3种白蛋白的荧光猝灭属于静态猝灭,且猝灭程度为HSABSAVOA。计算了不同温度下配合物与3种白蛋白间的结合常数(KA)、结合位点(n≈1)及相关热力学参数(ΔH0,ΔS0,ΔG0),确定配合物与3种白蛋白之间主要靠静电作用力结合。并且采用同步荧光光谱及三维荧光光谱法研究了配合物对HSA、BSA和VOA构象的影响。     

两种新的铕配合物的合成、表征及其光、热、电性质

以邻苯二甲酸酐、二苯胺、4-氨基安替吡啉和三氧化二铕为原料合成了Eu(PPA)3Phen和Eu(APA)3Phen.使用核磁和质谱对配体和配合物进行了表征,研究了紫外、荧光光谱、磷光寿命、热稳定性和电化学性质.结果表明,配合物的紫外吸收分别表现出生成它们各自配体的紫外吸收特征,Eu(PPA)3Phen和Eu(APA)3Phen在613nm处有很强的荧光发射,归属于Eu3+的5D0→7F2的特征发射,此外,在590nm处都有荧光发射.测得两种配合物粉末的磷光寿命,它们相差较大,Eu(PPA)3Phen有三个磷光寿命都约为0.0.45μs,Eu(APA)3Phen有两个磷光寿命都为650μs.热重分析表明,Eu(PPA)3Phen在30℃～260℃分解大约10%,而Eu(APA)3Phen在70℃～240℃分解大约5%.使用循环伏安法研究了Eu(PPA)3Phen和Eu(APA)3Phen的电化学性质,结果表明两者都约在0.86V处有不可逆的氧化电位值.     

Synthesis,crystal structure,and fluorescence of two dimeric europium（Ⅲ） complexes with 2-（trifluoromethyl）benzoate

Two complexes [Eu2（2-TFMBA）6（2,2′-bipy）2]·2H2O （1） and Eu2（2-TFMBA）6（1,10-phen）2 （2） （2-TFMBA=2-（Trifluoromethyl） benzoate; 2,2′-bipy=2,2′-bipyridine; 1,10-phen= 1,10-phenanthroline） were synthesized by solvent method and determined by X-ray diffraction analysis. Complex 1 crystallizes in monoclinic system with space group P21/c, whereas complex 2 crystallizes in triclinic system with space group Pi. Both are binuclear molecules with an inversion center. In complex 1, two center Eu^3＋ ions are linked together by four 2-TFMBA ligands in bidentate-bridging mode. Each Eu^3＋ ion is eight-coordinated with six O atoms from five 2-TFMBA ligands and two N atoms from one 2,2′-bipy molecule. In complex 2, two center Eu^3＋ ions are linked together by four 2-TFMBA ligands in two modes, namely, bidentate-bridging and tridentate-bridging. Each Eu^3＋ ion is nine-coordinated with seven O atoms from five 2-TFMBA ligands and two N atoms from one 1,10-phen molecule. The two complexes both exhibited strong red fluorescence under ultraviolet light, and the ^5D0→^7Fj （j=0-4） transition emissions of Eu^3＋ ion were observed in their emission spectra.     

Luminescence properties of polymers containing europium complexes with 4-tert-butylbenzoic acid

The binary europium complex EuL3 (L=4-tert-butylbenzoate) and ternary europium complexes EuL3TTA0.1 (TTA=2-thenoyltrifluoroacetone), EuL3DBM0.5 (DBM=dibenzoylmethane) and EuL3phen0.5 (phen=1, 10-phenan...     

Progresses in electroluminescence based on europium（III） complexes

The research on electroluminescence based on europium(III) complexes has come to an important phase. This article reviewed the progresses in photoluminescence and electroluminescence of Eu(III) complexes in recent years from the views of the design of Eu(III) complexes and optimization of device structures, and discussed some important factors influencing electroluminescence performance. The problems existing in the practical application such as the volatility and thermal stability of Eu(III) complexes in this area were discussed, and the possible corresponding solutions were briefly prospected.     

Synthesis,crystal structure and fluorescence property of 1-D europium complex with 2,3-difluorobenzoate

A new chain europium complex [Eu(2,3-DFBA)3·(H2O)2]n(2,3-DFBA=2,3-difluorobenzoate) was synthesized by solvent method.X-ray single-crystal diffraction analysis revealed that Eu3+ ions were linked through 2,3-DFBA groups via alternate bidentate-bridging and tridentate chelating-bridging coordination modes to form a one-dimensional(1-D) polymeric chain.Each Eu3+ ion is eight-coordinated by six O atoms of five 2,3-DFBA ligands and two water molecules.The abundant hydrogen bonds between chains resulted in a two...     

Syntheses,characterization, and luminescence of two lanthanide complexes [Ln2（acetate）6（HeO）4]·4H2O （Ln=Tb（1）, Sm（2））

Two dinuclear compounds [Ln2（acetate）6（H2O）4]-4H2O （Ln=Tb（1）, Sm（2）） were obtained by the hydrothermal reaction of Ln2O3 with malonic acid at 150 ℃. Both compounds were characterized by elemental analyses, infrared spectra, and single crystal X-ray diffraction. The results showed that complexes 1 and 2 were isomorphous and crystallize in triclinic space group P 1. The coordination geometry around Ln（Ⅲ） ions in the complexes 1 and 2 was a distorted tricapped trigonal prism with a nine coordination. In the crystal, the molecular organization was further stabilized by well-defined weak hydrogen bonding interactions between the neutral dinuclear molecular units that led to the formation of a three-dimensional network. The fluorescence properties of the two complexes 1 and 2 in organic solvents were also studied. The results show that the ligand acetate favored energy transfer to the emitting energy level of Tb（Ⅲ） in complex 1. Some factors that influence the fluorescent intensity were also discussed in the article.     

Synthesis, crystal structure and fluorescence of a new europium complex with 2-bromobenzoate and 2,2′-bipyridine

A new complex of {[Eu2(2-BrBA)6(2,2'-bpy)2]2.CH3CH2OH·H2O} (2-BrBA=2-bromobenzoate; 2,2'-bpy=2,2'-bipyridine) was prepared by solvent method and characterized with X-ray single-crystal diffraction, IR spectroscopy, UV spectrscopy, and fluorescence spectroscopy. The complex crystallized in triclinic crystal system, PT space group, with a=1.17196(4) nm, b=-2.36142(9) nm, c=2.59151(9) nm, a=113.266(2)°, β=101.100(2)°, and γ=94.400(2)°. Two independent dinuclear molecules were contained in the asymmetric unit. The two molecules were similar to each other. Each Eu(Ⅲ) ion was nine-coordinated with seven oxygen atoms from five 2-BrBA ligands and two ni-trogen atoms from 2,2'-bpy molecule. The carboxylate groups acted as bidentate-chelating, bidentate-bridging and chelating-bridging coor-dination modes. The complex adopted a distorted monocapped square-antiprism coordination geometry. Five peaks at 579, 591, 613, 652,and 697 nm appeared in the fluorescence spectrum, corresponding to 5D0→7F0, 5D0→7F1, 5D0→7F2, 5D0→7F3, and 5D0→7F4 transition emis-sions of the Eu(Ⅲ) ion, respectively.     

New complexes of heteroaromatic N-oxides with europium, uranyl and zinc ions

New solid complexes of europium,uranyl and zinc ions with N-oxides of 4-chloro-2,6-dimethylpyridine,quinoline and 4-meth-oxyquinaldinic acid in presence different anions were obtained and characterized by elemental and TG analyses,IR and luminescence spectra. The compounds are crystalline,hydrated or anhydrous salts with colours typical of metal ions.Thermal studies showed that in hydrated salts lattice or coordination water molecules are present.A role of different anions in the formation of various types of the complexes is presented.     

Study on fluorescence properties of rare earth complexes influenced by steric effect

The rare earth complexes Tb(o-BrBA)3,Tb(m-BrBA)3 and Tb(p-BrBA)3 were synthesized using o-,m-,p-bromo benzoic acids(2-bromo benzoic acid,3-bromo benzoic acid and 4-bromo benzoic acid) as ligand,respectively.The UV spectra showed that the absorption ability of Tb(m-BrBA)3 was the strongest.However,the fluorescent intensity of Tb(o-BrBA)3 was the weakest.The effect of the molecular structure,the energy level of Tb3+ and energy transfer efficiency from ligands to Tb3+ were discussed to explain the experimental results.The results indicated that,due to the large atomic radius of bromine,the steric effect caused by the different substitution bromine on the benzene ring might strongly affect the bond length formed by the coordination atoms and Tb3+.The longer the bond length was,the lower the efficiency of energy transfer was,and the weaker the fluorescent intensity was.     

丙烯酸稀土盐亚微米粒子制备及其荧光性能研究

用反相悬浮聚合方法 ,在超声分散的条件下 ,以氧化还原体系为引发剂、Span体系为乳化剂制备丙烯酸铕以及丙烯酸铕 (镧 )悬浮液。对体系的稳定性及稀土盐的荧光性能等进行了研究 ,讨论了镧离子和铕离子之间的荧光增强作用 ,并利用扫描电镜观察了粒子的形态和粒径