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)。     

铕(Ⅲ)-苯甲酰丙酮-邻菲啰啉配合物的合成及其荧光性质

为提高苯甲酰丙酮(BA)的Eu(Ⅲ)配合物的荧光强度,以邻菲啰啉(Phen)作为第2配体合成了三元混配配合物Eu(BA)3·Phen,并通过化学分析和元素分析确定了配合物的组成,通过FTIR谱对配合物进行了表征。荧光光谱数据表明,与相应的二元配合物Eu(BA)3·2H2O相比,Eu(BA)3·Phen的荧光强度提高了57%。     

新型稀土荧光材料的合成及性能研究

以巯基乙酸、间苯二甲酸为配体,分别与Eu(Ⅲ)、Pr(Ⅲ)、Dy(Ⅲ)在乙醇溶液中反应,生成稀土-巯基乙酸-间苯二甲酸三元配合物.用元素分析、红外光谱分析确定了配合物的化学组成.用热重、荧光光谱对3种配合物的性能进行了分析.结果表明:3种配合物热稳定性较高,Eu(Ⅲ)、Dy(Ⅲ)的配合物具有相对较强的荧光性能.     

稀土/PA6复合材料及纤维的制备及表征

利用制备的3种稀土配合物与PA6进行熔融共混,并进行熔融纺丝制备出不同稀土配合物/PA6复合材料及纤维。实验结果表明:稀土配合物与基体PA6之间存在一定的配位作用,使PA6对稀土配合物的发光具有一定的敏化作用;制备的复合材料具有较好的荧光性能,Eu(TTA)2Phen(IA)/PA6复合纤维的荧光性能最为突出。Eu(TTA)2Phen(IA)与Eu(TTA)2Phen(MA)的引入使复合纤维的力学性能较纯PA6纤维的力学性能有所提升。     

稀土铽三元配合物/橡胶复合材料的制备及荧光性能研究

采用稀土铽氧化物 (Tb4 O7)、邻苯二甲酸氢钾 (KHPht)和邻菲啉 (Phen)合成铽三元配合物Tb(Pht) 3Phen ,通过机械共混、交联成型制备Tb(Pht) 3Phen/NBR或Tb(Pht) 3Phen/甲基乙烯基硅橡胶复合材料。扫描电子显微镜观察表明 ,机械混合后稀土配合物的粒径减小 ;荧光性能测试表明 ,当Tb(Pht) 3Phen质量分数达到一定值时 ,复合材料的荧光性能比Tb(Pht) 3Phen配合物好 ,且随着Tb(Pht) 3Phen含量增大 ,复合材料的荧光强度增大 ,直到Tb(Pht) 3Phen质量分数大于 0 .2 3 1时才出现“浓度猝灭”现象 ;Tb(Pht) 3Phen质量分数相同时 ,Tb(Pht) 3Phen /甲基乙烯基硅橡胶体系的荧光强度比Tb(Pht) 3Phen/NBR体系大。     

含钐金属有机配合物的合成及其荧光性能的研究

以廉价的非荧光稀土离子镧掺杂钐作为中心离子,价廉易得的甲基丙烯酸甲酯(MMA)、1,10-邻菲罗啉(Phen)、水杨酸(SA)为配体反应生成一系列四元配合物SmL*L2Phen(L*=MMA,L=SA)。通过元素分析、X衍射分析、电镜、红外光谱、紫外光谱和荧光光谱对配合物进行了分析和表征。结果表明,稀土离子La的掺入能改变Sm的红光发光强度,在掺入量为70%(质量分数)时达到最佳。Sm-La系列有机配合物的特征发射峰位于582、616和662 nm处,与植物叶绿素光合作用的吸收红光波段吻合性较好。     

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。     

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。     

镝（Ⅲ）—BDPPPPD配合物的合成及其荧光性质

以二氧六环为溶剂，在pH约为7的条件下，分别以n(Dy^3 ):n(BDPPPD)=2:3和n(Dy^3 );n(BDPPPD);n(Phen)=2:3:2的量比（Phen为邻菲罗啉），合成了Dy（Ⅲ）的1，5－双（1′，3′－二苯基－5′－氧代吡唑－4′－基）－1，5－戊二酮（BDPPPD）的二元配合物Dy2(BDPPPD)3.6H2O和三元配合物Dy2(BDPPPP)3(Phen)2.2H2O,，收率为91．2％和89．6％。通过化学分析，元素分析和热分析确定了配合物的组成，通过FT－IR谱对配合物进行了表征，测定了配合物的荧光光谱，配合物的荧光发射峰位于481和576nm附近，分别相应于Dy^3 的^4F9/2→的^4F9/2→^6H15/2和4F9/2→6H13/2跃迁，说明配合物发射Dy（Ⅲ）的特征荧光，第二配体Phen具有荧光增强作用，三元配合物Dy2(BDPPPD)3(Phen)2.2H2O最大发射峰（576nm)的荧光强度是二元配合物Dy2(BDPPPD)3.6H2O的1．68倍。配合物具有较强荧光，说明BDPPPD的三重态能级与Dy^3 最低激发态（4F9／2）能级具有良好匹配，且其吸光系数较高，BDPPPD是Dy(Ⅲ）发光配合物的适宜配体。     

镝(Ⅲ)-BDPPPD配合物的合成及其荧光性质

以二氧六环为溶剂 ,在 pH约为 7的条件下 ,分别以n (Dy3+ )∶n (BDPPPD) =2∶3和n (Dy3+ )∶n(BDPPPD)∶n(Phen ) =2∶3∶2的量比 (Phen为邻菲罗啉 ) ,合成了Dy(Ⅲ)的 1,5 双 (1′,3′ 二苯基 5′ 氧代吡唑 4′ 基 ) 1,5 戊二酮 (BDPPPD)的二元配合物Dy2 (BDPPPD) 3·6H2 O和三元配合物Dy2(BDPPPD) 3(Phen) 2 ·2H2 O ,收率为 91 2 %和 89 6 %。通过化学分析、元素分析和热分析确定了配合物的组成 ,通过FT -IR谱对配合物进行了表征。测定了配合物的荧光光谱 ,配合物的荧光发射峰位于 481和 5 76nm附近 ,分别相应于Dy3+ 的 4 F9/2 → 6H15/2 和 4 F9/2 → 6H13/2 跃迁 ,说明配合物发射Dy(Ⅲ)的特征荧光。第二配体Phen具有荧光增强作用 ,三元配合物Dy2 (BDPPPD) 3(Phen) 2 ·2H2 O最大发射峰 (5 76nm)的荧光强度是二元配合物Dy2 (BDPPPD) 3·6H2 O的 1 6 8倍。配合物具有较强荧光 ,说明BDPPPD的三重态能级与Dy3+ 最低激发态 (4 F9/2 )能级具有良好匹配 ,且其吸光系数较高 ,BDPPPD是Dy(Ⅲ)发光配合物的适宜配体     

Synthesis and investigation of a photosensitive,europium-containing polymer

A series of europium complexes containing polymeric reactivity groups have been successfully synthesized using a simple method. Among them, Eu(DBM)₂(Phen)(MA), which has the best fluorescence properties and solubility, was polymerized with glycidyl methacrylate (GMA) for use as a novel UV-written polymer material. The Poly (GMA-co-Eu(DBM)₂(Phen)(MA)) containing different proportions of europium were prepared, and their spectroscopic properties were investigated in detail. Polymer films with optimum proportions (a molar ratio between GMA and Eu(DBM)₂(Phen)(MA) of 15) exhibited good UV light lithograph sensitivities, strong visible fluorescence intensities, high glass transition temperatures (T_g: >170 °C), good thermal stabilities (T_d: up to 295 °C) and solvent resistances after crosslinking. Micro patterns with smooth top surfaces were fabricated from the resulting polymer by using direct UV exposure and chemical development.     

Multi stimuli-responsive HPC-PAA/Eu(AA)3Phen complex nanogels and their decoration with 3-APBA for detecting glucose

In this paper, novel multi stimuli-responsive complex nanogels of hydroxypropylcellulose (HPC)-PAA/Eu(acrylic acid [AA])₃Phen were synthesized by radical polymerization method with HPC, rare earth complex (Eu(AA)₃Phen) and AA as raw materials, and the 3-aminophenylboronic acid (3-APBA) decorated nanogels (HPC-PAAPBA/Eu(AA)₃Phen) were fabricated via condensation of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride with 3-APBA. The microstructure, morphology and diameter of the nanogel were characterized by Fourier transform infrared spectrometer, UV–Visible spectrophotometer, transmission electron microscope, dynamic light scattering. Moreover, the fluorescence responsive performance of complex nanogels to temperature, pH value and glucose concentration was investigated by photoluminescence spectroscopy. The results showed that both of the as-prepared nanogels were uniform in size and had good monodispersity. The temperature and pH value had significant effects on the particle size and the fluorescence emission intensity of the HPC-PAA/Eu(AA)₃Phen complex nanogels; after decoration with 3-APBA, the obtained HPC-PAAPBA/Eu(AA)₃Phen nanogels showed excellent stimulus-response to glucose concentration.     

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.     

Copolymers of styrene with a quaternary europium complex

A complex of Eu³⁺, benzoate (BA), acrylate (AA), and 1,10‐phenanthroline (Phen) was synthesized in this work. The structure of Eu(BA)₂(AA)(Phen) was characterized with elemental analysis, FTIR, and UV spectroscopy. Copolymers containing rare earth complex were prepared via the copolymerization of Eu³⁺(BA)₂(AA)(Phen) with styrene. Semitransparent, luminescent polymer materials with high fluorescent intensity were obtained. The as‐synthesized materials were further characterized by means of IR and UV spectra, which indicated that they were copolymers instead of blends. The fluorescence spectra of the copolymers revealed the intense UV absorption characteristics of the rare earth complex present in the materials, as long as only a small portion of the complex was incorporated into the copolymers. Moreover, thermal analysis showed that the copolymer had excellent heat stability. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1506–1510, 2006     

Studies on preparation,structure and fluorescence emission of polymer-rare earth complexes composed of aryl carboxylic acid-functionalized polystyrene and Tb(Ⅲ) ion

4-(Chloromethyl) benzoic acid (CMBA) was first bonded onto the side chains of polystyrene (PS) via a polymer reaction, Friedel–Crafts alkylation reaction, and aryl carboxylic acid-functionalized polystyrene (PSBA) was generated. The functionalized polystyrene was used to prepare rare earth metal complexes. By using PSBA as macromolecule ligand, the binary polymer-rare earth complexes, PS-(BA)_n-Tb(Ⅲ), were prepared, and at the same time, ternary polymer-rare earth complexes, PS-(BA)_n-Tb(Ⅲ)-(Phen)_m, i.e. the mixed complexes in which both polymer-based aryl carboxylic acid and 1,10-phenanthroline as ligands were also prepared. The complexes were fully characterized using FTIR and proton NMR spectroscopy. Both ultraviolet absorption and fluorescence emission spectra for the complexes were recorded. The relationship between complex structure and the intensity of fluorescence emission was established. The experimental results show that the fluorescence emission from the central metal ion in the complex is strongly sensitized by the aryl carboxylic acid ligands chemically attached to the side chains of PSBA, and an apparent “Antenna Effect” is produced for these complexes. In the dilute solution of PSBA, the formed complex belongs to intramolecular complex. For the binary intramolecular complex, the apparent saturated coordination number of Tb³⁺ ion is 10, and here the binary complex has the structure of PS-(BA)₅-Tb(Ⅲ) and it has the strongest fluorescence emission among all of the binary complexes. When small-molecule Phen is added into the binary complex solution, the ternary complex PS-(BA)_n-Tb(Ⅲ)-(Phen)_m will be formed. As compared with the conventional ternary complexes PS-(BA)₁-Tb(Ⅲ)-Phen₂ and PS-(BA)₁-Tb(Ⅲ)-(Phen)₃ (the molar ratio of the central ion and the two ligands is conventional), the ternary complex with the structure of PS-(BA)₅-Tb(Ⅲ)-(Phen)₁ has the strongest fluorescence emission because of the complete coordination of the ligands to Tb³⁺ ion and the removal of the substituted water molecules around Tb³⁺ ion.     

Study on macromolecular lanthanide complexes (V): Synthesis,characterization, and fluorescence properties of lanthanide complexes with the copolymers of styrene and acrylic acid

In this study, the luminescent macromolecular lanthanide complexes Ln‐PSt/AA (Ln = Eu and Tb; St = styrene; AA = acrylic acid) have been synthesized, and an extensive characterization has been carried out by means of elemental analysis, FTIR, thermal analysis, and fluorescence determination. The results showed that the carboxylic groups on the chain of the polymers acted as bidentate ligands coordinated to lanthanide ions; and the coordination degree of ? COO^?/Ln³⁺ in the macromolecular complexes was closely dependent on both the pH value of the solution and the molar ratio of St to AA in the polymeric ligands. Thermal analysis manifested that these Ln‐PSt/AA (Ln = Eu and Tb) complexes had high thermal stability and solvent resistance, and these macromolecular complexes were highly crosslinked. The fluorescence determination indicated that Ln‐PSt/AA complexes could emit characteristic fluorescence with comparatively high brightness and good monochromaticity, and the fluorescence intensity changed with increasing lanthanide ions content. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

稀土铽三元有机配合物合成及荧光性能研究

合成了7种铽的稀土荧光有机材料——铽三元有机配合物,通过荧光光谱的测定,比较了第一配体的改变对配合物发光性能,尤其是发光强度的影响。实验表明,在以邻菲啉为第二配体的情况下,第一配体对铽三元配合物荧光强度影响顺序依次是:磺基水杨酸对甲基苯甲酸水杨酸苯甲酸对氨基苯甲酸乙酰丙酮,其磺基水杨酸为第一配体的铽三元有机配合物荧光强度最大,其相对强度为20000。     

铕(III)三元活性配合物/丙烯酸凝胶的制备

以氧化铕(Eu2O3)、邻菲罗啉(phen)和丙烯酸(AA)为原料,制备了含铕(III)三元活性配合物Eu(AA)3phen,与丙烯酸-丙烯酰胺凝胶体系进行UV共聚,制备了含铕水凝胶。研究了凝胶中Eu(AA)3phen含量对其吸水性、温敏性及荧光性能的影响,同时探讨了温度及溶胀时间对其荧光性能的影响。结果表明,随Eu(AA)3phen含量的增加,凝胶吸水率先增加后减少,荧光强度逐渐增强;对于特定的凝胶体系,其12 h溶胀度随温度增加而增加,凝胶的荧光强度随溶胀时间和温度增加而减弱。当Eu(AA)3phen的添加量为3.5%时,凝胶综合性能最佳:平衡溶胀度为631 g/g,4 h内吸水率达90%以上,荧光强度为175 a.u.。所研制的水凝胶在吸水及荧光性能方面对温度均具有良好的响应性。