铕配合物与苯乙烯共聚物的研究

Copolymers containing rare earth complex were prepared via copolymerizing complex Eu^3 (BA)2 (AA) (phen)) with styrene. A sort of semitransparent luminescent polymer material with high fluorescent intensity was obtained. They were characterized by means of IR and UV spectra, which show that they were copolymers, not blendings. The fluorescence spectra of copolymer indicated that it showed intense UV absorption characteristics of rare earth complex as long as only a little complex join in it. Moreover, thermal analysis showed that they had excellent heat-stability.     

铕配合物的合成及其荧光防伪油墨的制备

选用苯甲酸(BA)、噻吩甲酰三氟丙酮(TTA)、邻菲咯啉(Phen)作为配体合成了Eu(BA)3Phen三元配合物、Eu(BA)(TTA)2Phen四元配合物,将其作为荧光剂,制备了稀土荧光防伪油墨。红外光谱的分析表明配体与铕离子发生了配位。测定了配合物和荧光防伪油墨的荧光性能,发射波长为614 nm,制备的稀土荧光防伪油墨在可见光下印迹无色,在紫外灯下呈现明显红色荧光。     

铕配合物对胶印荧光防伪油墨荧光性能的影响

分别选用铕-β-二酮类三元配合物、铕-芳香羧酸类三元配合物、铕-β-二酮-芳香羧酸类四元配合物作为荧光剂,制备了荧光防伪胶印油墨,研究了荧光剂种类、荧光剂用量对油墨荧光性能的影响。结果表明:铕-β-二酮-芳香羧酸类四元配合物具备有发光强度高,热、光稳定性好等优点,适合制备荧光防伪油墨;该类油墨中荧光剂质量分数在8%左右较为适宜。     

含稀土配合物的甲基丙烯酸甲酯荧光性能研究

含稀土有机配合物的高分子材料综合了稀土材料和高分子材料的优异性能,在制备光学器件方面有广泛的应用前景.本文制备了含铕的噻吩甲酰三氟丙酮(TTA)和二苯甲酰甲烷(DBM)配合物的聚甲基丙烯酸甲酯(PMMA)体系,并考察了配合物含量、配体、小分子掺杂剂和PMMA分子量对体系荧光性能的影响.分析表明要想获得高效发光的稀土配合物高分子体系需要选用对称性较差,含氟取代基较多的配体,并找到合适的配体或小分子掺杂剂的含量,且尽量增大基体的分子量.     

羧酸类大分子稀土配合物的合成、表征及性能研究

通过先聚合再配合的方法成功制备了两种羧酸类大分子稀土铕配合物PAA-Eu和ST-AA-Eu,并将其与合成的小分子稀土配合物Eu(AA)3形成对比。经红外光谱初步表征发现稀土配合物已经配位成功且其配位数为6。分别采用凝胶渗透色谱(GPC)和等离子发射光谱(ICP)分析大分子稀土配合物的分子量与稀土铕的含量。由TG分析配合物的分解温度并了解其热稳定性能和组分,采用荧光激发发射光谱研究其荧光性能,采用SEM分析配合物与基质的相容性。结果表明,大分子稀土配合物的热稳定性稍差于小分子稀土配合物,其中ST-AA-Eu由于苯环的介入热稳定性能稍好。小分子稀土配合物Eu(AA)3的荧光强度明显要比大分子稀土配合物强,大分子稀土配合物PAA-Eu的荧光强度比ST-AA-Eu强,配合物都发红光;大分子稀土配合物与基质的相容性比小分子稀土配合物好。     

铕-芳香羧酸-丁二酸三元配合物的合成及荧光性能研究

以苯甲酸、对甲基苯甲酸、间氯苯甲酸、对氯苯甲酸、对羟基苯甲酸、对甲氧基苯甲酸为第一配体,丁二酸为第二配体合成了六种新的铕三元荧光配合物.通过元素分析、EDTA配位滴定分析、紫外光谱分析和红外光谱分析确定了标题配合物的组成及结构;采用热分析仪研究了标题配合物的热稳定性能;通过荧光光谱分析研究了标题配合物及对应二元配合物的发光性能.结果表明:标题配合物与对应的二元配合物相比发光强度大大提高.     

稀土(铕、铽)三元配合物的合成、表征与发光性能

合成了Eu(TFA)3(TPPO)2、Tb(TFA)3(TPPO)2三元配合物以及Eu1／2Tb1／2(TFA)3(TPPO)2三元双核配合物，并经元素分析、紫外-可见吸收光谱和红外透射光谱确认。研究了配合物的发光性质,发现了该三元体系配合物的摩擦发光现象,且三元双核配合物经摩擦发出明亮的白光。     

稀土铕有机配合物的研究进展及其应用

目的 介绍稀土铕有机配合物的原理、分类、应用及其最新研究进展,为高性能稀土铕配合物的研发提供一定的思路和依据。方法 通过查阅国内外学者近年来对稀土铕有机配合物的各种研究文献,对稀土铕有机配合物的主配体种类及应用进行整理总结。结果 稀土铕有机配合物的主配体有四大类,即β-二酮类、羧酸及羧酸盐类、有机高分子类与超分子大环类,该配合物主要应用于荧光材料、发光材料、磁性材料和生物等四大领域。结论 铕有机配合物的荧光性能良好,且高分子类配合物易加工成型;有机高分子类铕配合物可以结合Eu3+和高分子的优点,在提高其与聚合物材料相容性的前提下,有望成为一种新型的功能材料。     

稀土铕四元配合物纳米微晶的制备及性能

为了得到粒径均匀的纳米稀土铕四元配合物,采用化学沉淀法,进一步优化试验条件,制备Eu(BA)(TTA)2邻菲罗林纳米微晶,采用元素分析、红外光谱、热重分析、荧光光谱和透射电镜等方法对其进行表征和分析。结果表明,稀土铕四元配合物中高效率的能量传递是通过在2种不同第一配体之间形成的"协同效应"来完成,四元配合物中3种不同的配体可以更好地取代配位水;四元稀土配合物不仅发光性能优于常见的三元配合物,而且热稳定性好,粒径较小且均匀,可进一步掺入高分子形成功能性含稀土高分子聚合物;选用合适的缓冲溶液,在调节pH时将缓冲溶液缓慢地逐滴加入,可采取往反应体系中通氨气的方法,以使体系的pH改变较为平稳,生成的沉淀粒径较小且均匀。     

溶胀法制备含铕配合物的聚苯乙烯荧光微球

用溶胀剂溶胀单分散的聚苯乙烯微球,使稀土配合物铕-二苯甲酰甲烷-邻菲罗啉[Eu(DBM)3phen]渗透进入微球中,制备出含铕配合物的聚苯乙烯荧光微球。系统的研究了制备过程中溶胀剂的选择和用量、Eu(DBM)3phen的用量及溶胀时间对微球形貌和荧光强度的影响。用环境扫描电子显微镜、荧光显微镜和荧光分光光度计对微球的形貌、粒径和荧光强度进行了表征。结果表明,通过条件优化,可以制备出单分散的高亮度荧光微球,微球中铕配合物的最大含量为5.5%,并且荧光微球在pH=1～14范围内均有良好的稳定性,在生物医学领域有很好的应用前景。     

BSPDA-Eu配合物的合成及其时间分辨荧光性质

制备了一种含巯基的时间分辨荧光配体BSPDA（4，7-二巯基苯基1，10-菲罗啉-2,9-二羧酸）及其铕（Ⅲ）配合物，研究了铕配合物的荧光性质．结果表明，该巯基配体可与铕（Ⅲ）形成1：1和2：1具有时间分辨荧光特性的配合物，能发射出铕的特征谱线，其1：1与2：1的配合物具有数百微秒以上的荧光寿命，在相关的发射特征峰位处后者的寿命稍长于前者．这表明，在后者铕配合物中存在更强的配位作用和更有效配体对中心离子（即BSPDA到Eu^3＋）能量传递．     

稀土铕高分子荧光配合物的制备及性能研究

稀土配合物作为发光材料已广泛应用于众多领域,为了使材料获得更稳定更持久的发光性能,本文以N-乙烯基甲酰胺(NVF)和丙烯酰胺(AM)为共聚单体,水为溶剂,在高温、引发剂条件下经自由基溶液聚合制备出含有氨基、羧基等多种配位官能团的水溶性高分子聚合物两性聚乙烯胺(PVAm),并以此作为高分子配体,再辅以1,10-邻菲咯啉(phen)作为第二配体,用三价稀土离子铕(Eu)的盐溶液与之配位,制备出具有优良荧光效应的稀土配合物Eu(PVAm)_3phen荧光粉。对高分子配体PVAm进行IR、NMR等分析,找出配位官能团,并对稀土配合物的外观形貌进行荧光显微镜等观察分析,对配合物的结构进行XRD等表征,并分析其紫外光谱、荧光光谱、荧光余辉亮度。配合物在220～275 nm范围内对紫外光有较强的吸收,最大吸收峰在260 nm处。配合物在580、593、614、650 nm的4处有明显的荧光发射峰。     

In situ synthesis and luminescence characteristics of complexes of europium(III) with 4,6-diacetylresorcinol

The complexes of europium(III) with 4,6-diacetylresorcinol (H₂DAR) and a co-ligand (phen, bpy or 2,2′-bipyridine N,N′-dioxide (2,2′-bpyO₂)) were in situ synthesized in silica matrix via a two-step gel process. The formation of complexes in silica gel was confirmed by the luminescence excitation spectra. The silica gels that contain in situ synthesized europium complexes exhibit the characteristic emission bands of the Eu(III). The results show that there are two ways to enhance the emission intensity of the Eu(III): (i) synthesize the complex in silica matrix and (ii) synthesize the complex with a co-ligand, which coordinates with Eu(III) in the composite system and can efficiently transfer the energy from 4,6-diacetylresorcinol to the Eu(III). The order of the luminescence intensities of the complexes is: Eu₂(DAR)₃(phen)₂-(sol–gel) > Eu₂(DAR)₃(2,2′-bpyO₂)₂-(sol–gel) > Eu₂(DAR)₃ (bpy)₂-(sol–gel) > Eu₂(DAR)₃-(sol–gel) > pure Eu₂(DAR)₃·4H₂O.     

Formation, structure and wettability of fluorescent nanolayers of oligoperoxide europium complexes adsorbed to glass surface

Formation kinetics and the nanolayer structure are determined for fluorescent complexes, which are composed of oligoperoxide and europium (OP-Eu), and are adsorbed to glass from water-ammonia solutions. The effective surface fraction x modified by OP-Eu is evaluated (with the Cassie equation) from receding contact angles. Its temporal behavior is repeated by the average adlayer thickness d, determined from ellipsometry, indicating rapid adsorption followed by gradual desorption. The fraction x increases with d to saturate at ∼ 90% for 57 nm. Atomic Force Microscopy micrographs and refractive indices do not reflect simple composite surfaces. Therefore a thickness effect on OP-Eu surface energy is also advocated. Fluorescent microscopy confirms luminescent properties of OP-Eu, applicable for protein detection.     

Eu在羟基磷灰石中的掺杂及其发光性能研究

本文采用化学沉淀法制备了Eu3+掺杂的羟基磷灰石材料(HAP∶xEu),使用X射线衍射、红外光谱以及荧光光谱等对其结构及发光特性进行了研究。分析表明,制备得到的掺杂羟基磷灰石具有晶态结构,其红外谱中出现隶属于OH-、PO3-4的特征振动峰。光谱分析结果表明,在394nm波长激发下,掺杂Eu的羟基磷灰石样品的荧光发光强度和荧光寿命呈现随掺杂浓度的增加相反的变化趋势:发光强度增加6倍同时其荧光寿命却下降了约30%。此外,样品中电偶极跃迁与磁偶极跃迁强度之比(IR/IO)随Eu3+掺杂浓度增加表明Eu占据羟基磷灰石晶格中的CaⅡ不对称位点的比例大于占据CaⅠ对称位点的比例,并可受到掺杂量的影响。     

New complexes of europium and gadolinium with 2,4,6-trichlorophenyl acetoacetate as ligand

The synthesis, characterization and photoluminescent properties of new europium complexes with 2,4,6-trichlorophenyl acetoacetate (TCA) and 3-amino-2-carboxypyridine-N-oxide (picNO) ligands have been investigated. Results of the characterization are in agreement with the molecular formula proposed. The emission spectra at 77 K of the [Eu(TCA)₂(H₂O)₅]OH and [Eu(TCA)₂(picNO)(H₂O)₂]OH complexes, excited at 333 nm, display the typical transitions of the europium ion, ⁵D₀ → ⁷F_J (J = 0-4), indicating an efficient luminescence sensitization of this ion by the TCA ligand. The satisfactory agreement between experimental and theoretical absorption spectra of the organic part of the complexes suggests that the geometries optimized by the Sparkle model are correct. These results suggest these complexes as potential candidates as useful markers.     

Preparation and luminescence properties of sol-gel hybrid materials incorporated with europium complexes

Microporous silica gel has been prepared by the sol-gel method utilizing the hydrolysis and polycondensation of tetraethylorthosilicate (TEOS). The gel has been doped with the luminescent ternary europium complex Eu(TTA)₃·phen: where HTTA = 1-(2-thenoyl)-3,3,3-trifluoracetone and phen = 1,10-phenanthroline. By contrast to the weak f-f electron absorption bands of Eu³⁺, the complex organic ligand exhibits intense near ultraviolet absorption. Energy transfer from the ligand to Eu³⁺ enables the production of efficient, sharp visible luminescence from this material. Utilizing the polymerization of methyl methacrylate or ethyl methacrylate, the inorganic/polymer hybrid materials containing Eu(TTA)₃·phen have also been obtained. SEM micrographs show uniformly dispersed particles in the nanometre range. The characteristic luminescence spectral features of europium ions are present in the emission spectra of the hybrid material doped with Eu(TTA)₃·phen.     

Molecular complexes of 3-hydroxypyridine with nitro-substituted aromatic and heterocyclic carboxylic acids

Four organic salt complexes of 3-hydroxypyridine (3-HP) with nitro-substituted aromatic and heterocyclic carboxylic acids have been prepared and their X-ray crystal structures reported. These complexes are 3-hydroxypyridinium 5-nitrofuran-2-carboxylate 1, 3-hydroxypyridinium 4-nitrobenzoate 2, 3-hydroxypyridinium 2,4-dinitrobenzoate 3, and 3-hydroxypyridinium 3,5-dinitrobenzoate 4. The hydrogen-bonding networks in each are dominated by interactions from both the protonated heterocyclic nitrogen and the 3-hydroxy group on 3-HP to the carboxylate oxygens. The principal structural unit in complexes 1 and 3 is a tetramer consisting of two of each component molecule, whereas in complexes 2 and 4 the hydrogen-bonded polymers are observed. In all cases additional CH···O interactions to the nitro oxygens are present and add to the hydrogen-bonding array. A review of three previous 3-HP salt structures as well as the four presented in this paper reveals that the hydrogen-bonding distances between nonhydrogen atoms from the heterocyclic nitrogen of 3-HP is slightly longer than that from the 3-hydroxy group [av. 2.658(5) and 2.594(5)].