四元羧酸稀土配合物的合成与表征

在水溶液中合成了铕和铽的四元羧酸稀土配合物。通过红外光谱,元素分析,热分析及荧光光谱,对其组成及其荧光性能进行了表征。结果表明两种稀土配合物具有较好的荧光性质。     

2,3,5-吡啶三酸与稀土铕配合物的合成及发光性质

采用水作溶剂,用2,3,5-吡啶三酸与稀土铕的氯化物反应合成了一种配合物,通过EDTA络合滴定分析,确定了配合物中铕离子的含量;并对配合物进行了熔点、红外光谱测定,测试了固态铕配合物的荧光激发和发射光谱。结果表明,该配合物具有良好的光致发光性质。     

N-(2-羟苄基)-DL-丙氨酸铕(Ⅲ)配合物的合成及荧光性质

以发光的三价铕离子为中心体,N-(2-羟苄基)-DL-丙氨酸(H2sala)和1,10-邻菲咯啉(phen)为配体,在混合溶剂中合成了二元铕配合物[Eu(sala)(H2O)4].Cl和三元铕配合物[Eu(sala)(phen)2].Cl。通过元素分析、摩尔电导、红外光谱和热重分析等手段确定了配合物的组成及结构。荧光光谱数据表明,三元配合物的荧光强度高于二元配合物。     

二元、三元二苯甲酰甲烷铕配合物的荧光研究

以发光的三价铕离子为中心体，二苯甲酰甲烷（DBM）、邻菲罗啉（Phen)和2，2‘-联吡啶（Dipy）为配体，在无水乙醇溶液中反应，合成了二元铕配合物Eu(DBM)3和三元配合物Eu(Phen）（DBM）3及Eu(Dipy)（DBM)3,经元素分析，确定了其组成。红外光谱及荧光光谱测试表明，配体中氧原子和氮原子均与铕（Ⅲ）离子配位，三元配合物的荧光强度高于二元配合物，三元配合物中含吡啶的配合物Eu(Dipy)(DBM)3荧光强度又高于含邻菲罗啉的配合物Eu(Phen)-(DBM)。     

含有萘酰亚胺单元的铕配合物合成及其发光性能研究

通过在邻菲哕啉中性配体上引入萘酰亚胺发色团，合成了新型含有萘酰亚胺单元的铕配合物Eu（DBM）3（PNI—phen）．通过控制激发，可以得到具有萘酰亚胺和Eu^3＋特征友射的荧光光谱．通过荧光光谱和激发光谱研究了铕配合物的能量传递及发光机制．     

配合物Eu（Sal）2（phen）2（NO3）的合成及荧光性能的研究

用硝酸铕、水杨酸与邻菲罗啉为原料合成了配合物Eu(Sal)2(phen)2(NO3),考察了配体用量和溶剂用量等因素对反应的影响.通过元素分析、红外光谱和紫外光谱确定了配合物的组成及结构,并通过荧光光谱对其荧光性质进行了研究.     

丙烯酸酯类聚氨酯/衣康酸铕光致发光材料的制备及性能

以衣康酸为配体,稀土铕离子(Eu~(3+))为中心离子,合成出衣康酸铕配合物,将此配合物与丙烯酸酯类聚氨酯大分子单体反应,制备出丙烯酸酯类聚氨酯/稀土铕光致发光材料(Eu-PUA)。通过傅里叶变换红外光谱、荧光光谱、热重分析和动态热力学分析表征了中间体衣康酸铕配合物以及所合成的Eu-PUA的结构和性能。结果表明,衣康酸铕配合物含有活性官能团双键(C=C),可与丙烯酸酯类聚氨酯大单体中的双键(C=C)反应,该配合物具有较好的荧光性能和热稳定性。衣康酸铕对Eu-PUA热稳定性能的影响很小,Eu-PUA在250℃之前几乎没有失重。随着衣康酸铕含量的增加,Eu-PUA材料的玻璃化转变温度有所提升,荧光强度先增加后减小,透明性逐渐变差。当衣康酸铕质量分数为2%时,材料的荧光强度最强。     

双配体稀土配合物的合成及长寿命荧光性质研究简

分别以β-二酬类化合物为第一配体、菲类化合物为第二配体,合成了八种稀土铕、铽配合物。用红外光谱对八种配合物进行了表征,实验考察了配合物在有机溶剂中的溶解性及其长寿命荧光发光性能。     

镧对铕配合物的发光影响

本实验用氯化铕、氯化镧与对羟基苯甲酸铵和邻菲罗啉合成了异核稀土配合物。研究了它们的发光光谱，由Eu:La的加入量的不同测出其荧光光谱的强度变化规律，随着不发光La^3 的加入量增加，其发光稀土Eu^3 的荧光强度增加。     

Eu3+-2-噻吩甲酰三氟丙酮、三苯基氧膦三元配合物的合成应用

以二苯甲酰甲烷和三苯基氧膦为混合配体,合成了三元配合物Eu(HTTA)_3(TPPO)_2。对配合物进行了氢谱、红外结构表征。配合物经紫外光谱、荧光光谱、荧光寿命、荧光量子效率等分析,表明配合物可以发出很强的铕的特征红色荧光,其荧光寿命为753.41μs,荧光量子效率为83.00%。配合物作为红光材料,制成白光LED器件,进行色温和色坐标的测定,表明该材料具有一定的应用前景。     

Facile fabrication of novel Eu‐containing copolymer and luminescent properties

A new Eu‐containing copolymer was successfully fabricated through two steps. First, the Eu‐containing monomer was synthesized from 4‐Vinylbenzoic acid and europium ion (Eu³⁺) complex, which rare‐earth ions connect with the ligand by covalent bands. Next, the copolymer was obtained by free‐radical copolymerization of Eu‐containing monomer with methyl methacrylate using 2, 2′‐azobis(isobutyronitrile) (AIBN) as initiator at low temperature. Infrared spectroscopy, gel permeation chromatography and scanning electron microscopy were applied to characterize the structure of the polymer. UV‐visible absorption/photoluminescence spectra and fluorescence spectra were taken to valuate the photophysical properties of the obtained Eu‐containing copolymer. The experimental result shows that the strong luminescence of europium ions substantiates optimum energy match and effective intramolecular energy transfer between the triplet state energy of coordination complex and the emissive energy level of the rare‐earth ions. A study of the dependence of emission intensities of the Eu‐containing nanoparticles on the Eu content showed that the emission intensities increased nearly linearly with increasing Eu content. In addition, no significant emission concentration quenching phenomenon was observed at the Eu content of 0–4.61 mol%. The hybrid material systems can be expected to have potential applications in light conversion materials. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

对羟基苯甲酸稀土(铕)配合物及其荧光纤维的制备

合成了Eu3+与对羟基苯甲酸、1,10-邻菲啰啉(phen)的具有新型结构的稀土配合物。通过TEM、元素分析、IR、TG及荧光光谱分析对其表观形貌、粒径、组成结构及荧光性能进行了分析表征。结果表明:对羟基苯甲酸稀土配合物呈球状,粒径在100nm左右;配合物具有良好的热稳定性。配合物的荧光发射峰分别与稀土铕5D0→7FJ(J=0,1,2,4)的跃迁相对应,最强发射峰位于616.3nm处。将制得的配合物与聚丙烯树脂进行熔融纺丝,制得稀土荧光纤维。测试结果表明:纤维具有优异的荧光性能,最强发射峰位于618nm处,是Eu3+的特征红色发射谱带。     

Spectroscopic Properties and Energy Transfer Mechanism of Er^3＋/Yb^3＋/Ce^3＋ Codoped Tellurite-based Glasses

为进一步揭示多稀土离子共掺低声子能量玻璃中Er3＋的光谱特性及其发光机理,采用高温熔融法制备了Er3＋/Yb3＋/Ce3＋共掺组分为（72.5–x）TeO2–20ZnO–5La2O3–0.5Er2O3–2Yb2O3–xCe2O3（x=0,0.4,0.7,1.0,摩尔分数x%）的碲酸盐玻璃,通过测量吸收光谱、荧光光谱和无掺杂样品的Raman光谱,以及计算相应能级间的吸收截面和受激发射截面,研究并分析了Yb3＋和Ce3＋离子掺杂对于Er3＋的1.55μm波段荧光特性的影响。结果显示：Yb3＋和Ce3＋的引入能显著增强975nm泵浦下Er3＋的1.55μm波段荧光强度。分析表明：Er3＋在1.55μm波段荧光强度的增强主要归结于Yb3＋/Yb3＋、Yb3＋/Er3＋离子间的共振能量传递过程以及基于单声子和双声子辅助的Er3＋/Ce3＋离子间的能量传递过程,并通过计算得到了相应稀土离子间的能量传递微观参数和声子所作的贡献比。     

稀土Eu~(3+)与牛血清白蛋白配合物合成及其分子光谱表征

研究了稀土 Eu3 +与牛血清白蛋白 ( BSA)的固体配合物合成方法 ,产物经傅里叶红外光谱分析表明 :Eu3 + 与牛血清白蛋白羧基的氧和胺基或酰胺基的氮形成强烈配位的配合物。在模拟生理条件下研究了 Eu3 + 与 BSA的结合性质。荧光光谱表明 :Eu3 + 与 BSA形成 2 .75∶ 1的配合物 ,表观配位常数为 lg K=1 2 .2 6     

稀土Eu光转换材料的合成

以聚二甲基硅氧烷（PDMS）为配体,以三苯基氧膦（TPPO）为协同配体,合成稀土铕高分子透明薄膜。用荧光、红外光谱对薄膜进行表征。结果表明薄膜具有良好的荧光性质,并且发现Eu^3＋直接键合到PDMS链中的氧原子上。荧光光谱表明配合物同时具有PDMS和Eu^3＋的特征发射。     

稀土紫外荧光防伪油墨的制备

合成了稀土有机配合物Ｅｕ（ＴＦＡ）_３ｐｈｅｎ、Ｅｕ（Ｙ）（ＴＴＡ）_３ｐｈｅｎ,该类配合物能在紫外光激发下（λ_（ｅｘ）＝３８６ｎｍ）发出强可见光红光（λ_（ｅｍ）＝６１９ｎｍ）,稀土元素Ｙ对Ｅｕ（ＴＴＡ）_３ｐｈｅｎ具有荧光增强作用,以增强稀土荧光粉Ｅｕ（Ｙ）（ＴＴＡ）_３Ｐｈｅｎ制备紫外荧光防伪油墨。     

Local microstructure characterization of rare earth‐doped PMMA with low‐ion content by fluorescence EXAFS

Fluorescence‐extended X‐ray absorption fine structure (EXAFS), and emission spectrum and excitation spectrum (ESES) were used to characterize the local structure of rare earth‐doped poly(methyl methacrylate)s (Re‐PMMAs) with ion concentration of 600–1000 ppm. Fluorescence EXAFS shows that the chemical state of Sm in Sm‐PMMA is the same as that in Sm₂O₃ and samarium octanoate (SOA), while that of Eu in Eu‐PMMA is different from that in Eu₂O₃ and europium octanoate. ESES also proves the concomitance of Eu²⁺ with Eu³⁺ ions in Eu‐PMMA. And, the almost identical peak positions of Eu L₃ edge at ～6976.7 eV in fluorescence EXAFS of Eu‐PMMA with various Eu content suggests the proportions of Eu²⁺ to Eu³⁺ are the same in these samples. The simulation of fluorescence EXAFS shows that the first‐shell coordination number of Sm³⁺ in Sm‐PMMA is 9.12, and the average first‐shell distance around Sm³⁺ in Sm‐PMMA is 2.43 Å. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1294–1298, 2006     

Modifying polysulfone into a bidentate Schiff base type macromolecular ligand and study on photoluminescence property of polymer–rare earth complexes of Eu(III) and Tb(III)

Chloromethylated polysulfone (CMPSF) was directly transformed into aldehyde (AL) group-functionalized polymer via Kornblum reaction, and then polysulfone was modified to a bidentate Schiff base (BS) type macromolecular ligand, PSF-ASB, via Schiff base reaction with 3-aminopyridine as reagent. Afterward, luminescent binary and ternary polymer-rare earth complexes, PSF-(ASB)₃-Eu (III) and PSF-(ASB)₃-Eu(III)-(Phen)₁ (o-phenanthroline, Phen), were prepared. The macromolecular ligand PSF-ASB and the complexes were fully characterized by FTIR, ¹H-NMR, UV spectroscopy and TGA. The photoluminescence properties and mechanisms of the complexes were investigated in depth. The experimental results show that the macromolecular ligand PSF-ASB itself emits strong fluorescence. However, after coordinating to Eu(III) ion, its fluorescence intensity weakens remarkably, implying that there occurs an intramolecular energy transfer. The complexes of Eu(III) ion exhibit stronger characteristic fluorescence emission of Eu(III) ion, whereas the complex of Tb(III) ion has no photoluminescence property, indicating that the bonded ligand ASB can effectively sensitize the fluorescence emission of Eu(III) ion and suggesting that the triplet state energy of the bonded ligand ASB is well matched with the resonant state level of Eu(III) ion. More importantly, relative to general polymer-rare earth complexes, for these luminescent polymer-rare earth complexes prepared in this study, the backbone of the macromolecular ligand PSF-ASB also takes part in the sensitization towards Eu(III) ion because of that half of aryl rings of a greater π bond conjugate system of ASB comes from PSF skeleton, displaying a great difference with other luminescent polymer-rare earth complexes.     

水热法制备Y2O3:Eu3+微米棒及其荧光性能表征

利用水热法制备了Y2O3和Y2O3:Eu3+,探讨了反应温度、反应时间及氢氧化钠溶液浓度对产物晶型的影响,确定了生成较好晶型的反应条件为：反应温度180℃,反应时间24 h,氢氧化钠溶液浓度2 mol/L. 研究了Y3+和Eu3+的配比对Y2O3:Eu3+荧光性能的影响. 结果表明,当n(Y3+):n(Eu3+)的比例为100:5时,其荧光强度最佳. TEM分析表明,Y2O3:Eu3+粉末具有直径约0.2~0.6 mm、长度为几到十几微米的棒状结构.     

聚苯乙烯-聚4-乙烯基吡啶-稀土铕(Ⅲ)发光配合物的微观结构及荧光性能表征

含共轭结构氮杂环的非离子嵌段共聚物能与铕(Ⅲ)络合反应形成发光配合物,研究了该发光配合物的配位结构及其荧光性能。以聚苯乙烯-聚4-乙烯基吡啶(PS-b-P4VP)作为高分子配体,以邻菲罗啉(Phen)作为小分子配体,通过吡啶环的氮原子与Eu(Ⅲ)离子配位发生络合反应形成了以网状的Eu(Ⅲ)-P4VP核层以及PS链段为壳层的共聚物-稀土配合物,通过电子透射电镜(TEM)分析了其微观形态结构。用荧光分光光度计分别表征了嵌段聚合物-稀土铕(III)配合物不同链段的荧光发光强度并且进行了荧光强度的对比。此外,还研究了不同的Eu(Ⅲ)离子浓度对荧光强度的影响,得到了制备共聚物-稀土配合物荧光的最佳Eu(Ⅲ)离子浓度。