Eu(Ⅲ)烟酸、邻菲咯啉三元配合物的合成、光谱性质及荧光性能的研究

本文报道了Ｅｕ（Ⅲ）与烟酸（ＨＬ）及邻菲咯啉（Ｐｈｅｎ）形成的三元固态配合物。通过元素分析、热谱分析和摩尔电导确定其化学组成为ＲＥ（Ｐｈｅｎ）Ｌ３,并利用红外、紫外光谱、核磁共振谱和Ｘ－射线粉末衍射对配合物进行了表征。研究了配合物的荧光性质。     

Eu-β-二酮配合物分子内能量传递的光声光谱研究

报道了Ｅｕ（Ⅲ）的乙酰丙酮（ＡＡ）、六氟乙酰丙酮（ＨＦＡ）、噻吩甲酰三氟丙酮（ＴＴＡ）固体配合物的光声光谱。本文从无辐射跃迁角度研究Ｅｕ－β－二酮配合物分子内能量传递过程。Ｅｕ－ＡＡ配合物、Ｅｕ－ＨＦＡ配合物、Ｅｕ－ＴＴＡ配合物无辐射跃迁几率依次减弱,原因在于配体经三重态能量转移且敏化Ｅｕ离子荧光的效率依次增大,可从配体与Ｅｕ离子能级之间是到解释     

邻啡啰啉─吡啶2，6二甲酸铕二、三元配合物的NMR研究

报道了稀上铕（Ｅｕ３＋）与吡啶－２，６－二甲酸（Ｈ２ＤＰＣ）及邻啡啉（Ｐｈｅｎ）形成的二元和三元固体配合物的制备．对它们进行了元素分析，确定该配合物的组成为二元Ｎａ３［Ｅｕ（ＤＰＣ）３］２Ｈ２Ｏ和三元ＮａＥｕ（ＤＰＣ）２·４Ｈ２Ｏ，对上述配合物的结构作了核磁共振氢谱（１ＨＮＭＲ）、碳谱（１３ＣＮＭＲ）和氮谱（１４ＮＮＭＲ）及红外光谱（ＩＲ）的研究．吡啶－２，６－二甲酸中的羧基以单齿配位（整个分子为三齿配位）．二、三元配合物中铕的配位数分别为９和８．     

Ln(Ⅲ)-Ni(Ⅱ)与双水杨醛缩乙二胺席夫碱异核配合物的合成与波谱

合成了双水杨醛缩乙二胺席夫碱（ＳＡＬＥＮ）与镍的配合物Ｎｉ３（ＳＡＬＥＮ）２（ＮＯ３）６·Ｈ２Ｏ及镧系镍的异核配合物Ｌｎ２Ｎｉ３（ＳＡＬＥＮ）６（ＮＯ３）１２·Ｈ２Ｏ（Ｌｎ＝Ｌａ，Ｎｄ，Ｓｍ，Ｇｄ，Ｙｂ，Ｙ）．以紫外、红外光谱、磁化率，特别是１ＨＮＭＲ及ＥＰＲ波谱等方法研究了它们在组成、结构和配位等方面的异同．ＧｄＮｉＳＡＬＥＮ配合物的ＥＰＲ谱表明其在低温ＴＨＦ中呈“单峰效应”．文中讨论了配合物在不同溶剂中峰宽的相对关系、配合物晶体场强度及Ｇｄ３＋周围局部对称性问题     

邻菲绕啉对Tb（Ⅲ）、Eu（Ⅲ）水杨酸二元配合物荧光强度的影响研究

通过分析邻菲绕啉与Ｔｂ（Ⅱ）、Ｅｕ（Ⅱ）水杨酸二元、三元配合物的多种谱留数据、证实由于邻菲绕啉的最低三重态与Ｔｂ（Ⅱ）、Ｅｕ（Ⅱ）离子的第一激发态能级差的不同，使得邻菲绕啉够增强Ｅｕ（Ⅱ）离子的水杨酸二元配合物的荧光强度而减弱Ｔｂ（Ⅱ）离子的水杨酸二元配合物的荧光强度．     

铜（II）盐催化氯代苯酚聚合反应机理的研究

本文研究了铜（Ⅱ）盐催化氯代苯酚的聚合反应，利用元素分析、ＩＲ（红外）和ＮＭＲ（核磁共振）对聚合物的结构进行了鉴定。分离出了聚合过程中所形成的氯代苯氧－铜（Ⅱ）配合物中间体，并利用元素分析、ＥＳＲ（电子自旋共振）研究了该配合物中间体。该配合物中间体在苯中回流得到相应的聚合物。ＥＳＲ研究该配合物中间体发现在室温下有苯氧自由基的存在，并在１２０℃热分解过程中发现苯氧自由基的ＥＳＲ谱随着测定时间的延长强     

铕与对甲基苯甲酸及2,2‘—联吡啶三元配合物的谱学研究

元素分析表明稀土铕（Ｅｕ＾３＋）与对甲基苯甲酸（Ｐ－ＭＢＡ）及２，２’－联吡啶（ｄｉｐｙ）形成的三元配合物组成为Ｅｕ２（Ｐ－ＭＢＡ）６（ｄｉｐｙ）２对甲基苯甲酸，２，２’－联吡啶均以双齿配位，中心铕离子的配位数为８，两个铕离子通过四个对甲基苯甲酸基桥联，形成双核配合物，对该配合物的结构作了核磁共振氢谱，碳谱及红外光谱的研究。     

Eu(p-PBA)_3phen1/2H_2O的高分辨光谱和Raman光谱Eu(p-PBA)3phen1/2H2O的高分辨光谱和Raman光谱*张颖唐波金林培(北京师范大学化学系,北京100875)吕少哲黄世华(中国科学院激发

配合物Ｅｕ（ｐ－ＰＢＡ）３ｐｈｅｎ１／２Ｈ２Ｏ（ｐ－ＰＢＡ：对苯基苯甲酸酸根离子；ｐｈｅｎ：邻菲咯啉）在紫外光激发下，能发出很强的红色荧光．以Ｅｕ（Ⅲ）离子为光谱探针，７７Ｋ下测得其高分辨激发和发射光谱，选择激发配合物的５Ｄ０能级，得到两组不同的发光光谱，表明配合物中Ｅｕ（Ⅲ）离子有两种不同的化学环境．配合物的喇曼光谱中，羧基阴离子的反对称伸缩振动和对称伸缩振动谱带是明显分裂和带肩峰的宽带，说明配合物中羧基同时存在多种配位方式     

铕与对甲基苯甲酸及2，2＇－联吡啶三元配合物的谱学研究

元素分析表明稀土铕（Ｅｕ~（３＋））与对甲基苯甲酸（Ｐ－ＭＢＡ）及２．２＇－联吡啶（ｄｉｐｙ）形成的三元配合物的组成为Ｅｕ_２（Ｐ－ＭＢＡ）_６（ｄｉｐｙ）_２，对甲基苯甲酸、２，２＇－联吡啶均以双齿配位，中心铕离子的配位数为８，两个铕离子通过四个对甲基苯甲酸基桥联，形成双核配合物，对该配合物的结构作了核磁共振氢谱、碳谱及红外光谱的研究。     

稀土（Eu^3＋,Tb^3＋）含氮杂环配合物的合成,表征及其荧光性质

在无水乙醇溶液中分别合成了Ｅｕ＾２＋离子、Ｔｂ＾３＋离子与２，２‘－联吡啶、１，１０－邻菲罗啉押种配合物，研究了配合物的荧光性质，由于Ｐｈｅｎ含有较大范围的共轭π键和较好的刚性平面，含Ｐｈｅｎ配合物的荧光强度均要比配合物的强；配合物的高分辨荧光光谱表明，Ｅｕ＾３＋离子在Ｅｕ（Ｄｉｐｙ）２Ｃｌ３’２Ｈ２Ｏ和Ｅｕ（Ｐｈｅｎ）２Ｃｌ３．２Ｈ２Ｏ配合物中处于Ｃ１或Ｃ２或Ｃ５的对称性位置。     

铕铽共掺稀土聚合物的光谱分析及发光性能研究

合成了一种新型的稀土配合物Eu_0.5Tb_0.5(TTA)₃Phen,并采用原位乳液聚合法进一步制备了Eu_0.5Tb_0.5(TTA)₃Phen/PMMA稀土聚合物。利用红外光谱仪(IR)、电子探针X射线能谱仪等对其结构进行了表征,利用扫描隧道电子显微镜(SEM)、荧光光谱仪(FS)等研究了其微观形貌,并探讨了其发光性能。结果表明,聚合物中PMMA与稀土部分Eu_0.5Tb_0.5(TTA)₃Phen通过键合的方式结合, 仍保持Eu0.5Tb_0.5(TTA)₃Phen原有的发光特性;在365 nm紫外光的激发下,产生发光峰在611.8 nm附近、谱线带宽为10.4 nm的红光发射,发光亮度高,色纯度高;Eu_0.5Tb_0.5(TTA)₃Phen/PMMA具有良好的发光性能,其发光强度与MMA加入的含量有关。     

偏苯三甲酸铕（Ⅲ）系列四元配合物的合成及相关性能研究

合成了Eu（Ⅲ）与偏苯三甲酸（TLA）、2-噻酚甲酰三氟丙酮（HTTA）和邻菲罗啉（Phen）形成的两个新的四元配合物。运用元素分析、红外光谱、扫描电镜、热重与荧光光谱等手段对它们进行了系统的表征。研究结果表明,偏苯三甲酸与2-噻酚甲酰三氟丙酮Eu（Ⅲ）和邻菲罗啉形成的四元配合物,具有比偏苯三甲酸Eu（Ⅲ）和邻菲罗啉形成的三元配合物更强的荧光强度与更宽的紫外激发,比配合物Eu（TTA）3Phen更好的热稳定性。得到了两种热稳定性较好的鲜艳红色荧光材料。     

Preparation of polymer–rare earth complex using salicylic acid-containing polystyrene and its fluorescence emission property

Salicylic acid (SA) was first bonded onto the side chains of polystyrene (PS), obtaining functional macromolecule SAPS. Using the salicylic acid-containing polystyrene as a macromolecular ligand, a polymer–rare earth complex, SAPS–Eu(III), was prepared. The structure of SAPS–Eu(III) was characterized, and the fluorescence properties of SAPS–Eu(III) were mainly investigated. The experimental results show that the complex SAPS–Eu(III) has fine chemical stability because of the bidentate chelating effect of salicylic acid ligand. More important, the ligand SA on the side chains of PS can strongly sensitize the fluorescence emission of the center ion, Eu³⁺ ion, and it enables the complex SAPS–Eu(III) to produce the apparent “Antenna Effect”. In the diluted solution of the functional macromolecule SAPS, the formed complex SAPS–Eu(III) belongs to an intramolecular complex, or an intrachain complex. For the binary intramolecular complex SAPS–Eu(III), the apparent saturated coordination number of SA of SAPS towards Eu³⁺ ion is equal to 10, and here the binary intrachain complex SAPS–Eu(III) has the strongest fluorescence emission. On this basis, small-molecule 1,10-phenanthroline (Phen) acting as a co-ligand is added and the ternary complex SAPS–Eu(III)–Phen will be formed. As long as a small amount of Phen is added (in the molar ratio 1:1 (n(Phen):n(Eu))), the coordination of the two kinds of ligands, SA of SAPS and Phen, to Eu³⁺ ion will reach complete saturation, and here the fluorescence emission of the ternary complex will be further enhanced via the complementary coordination effect in comparison with that of the binary complex SAPS–Eu(III).     

Synthesis and luminescent properties of complexes of Eu(III) with 2-thienyltrifluoroacetonate, terephthalic acid and phenanthroline

This work reports the synthesis and luminescent properties of complexes of europium(III) with 2-thienyltrifluoroacetonate (HTTA), terephthalic acid (TPA) and phenanthroline (Phen), in the solid state. The new complexes were characterized by elemental analysis, infrared (IR) spectroscopy, scanning electronic microscopy (SEM) and thermal stability analysis. Both binuclear complex Eu₂(TPA)(TTA)₄Phen₂ and polynuclear complex Eu(TPA)(TTA)Phen present better thermal stability than the mononuclear complex Eu(TTA)₃Phen does. The formation of the binuclear/polynuclear structure of the complexes appears to be responsible for the enhancement of the thermal stability. The emission spectra show narrow emission bands that arise from the ⁵D₀→⁷F_J (J=0-4) transition of the Eu³⁺ ion. The spectral data of the complexes Eu(TPA)(TTA)Phen and Eu₂(TPA)(TTA)₄Phen₂ present only one sharp peak in the region of the ⁵D₀→⁷F₀ transition indicating that only one Eu³⁺ ion species is present in each sample. In addition, the luminescence decay curves of the complexes Eu(TPA)(TTA)Phen and Eu₂(TPA)(TTA)₄Phen₂ fit a single-exponential decay law. The values of quantum efficiencies of the emitting ⁵D₀ level for the complexes Eu(TPA)(TTA)Phen and Eu₂(TPA)(TTA)₄Phen₂ are 29% and 28%, respectively.     

Assemblies, characterization, and luminescent enhancement of organized molecular films based on rare earth complexes

Langmuir-Blodgett (LB) films of different molar percentages of Eu(TTA)₃Phen (TTA=2-thenoyltrifluoroacetone; Phen=1,10-phenanthroline) with Gd(TTA)₃Phen coexisting with arachidic acid (AA) (complexes:AA=1:l, in molar ratio) were fabricated and the luminescence enhancement of Eu(III) in the films was studied in this investigation. The monolayers and LB films were characterized by π-A isotherms, fluorescence microscopy, UV-vis spectroscopy and low-angle X-ray diffraction. High-quality LB films and strongly luminescent films were obtained. It was learned from the present study that an efficient intermolecular energy transfer occurred from Gd(TTA)₃Phen to Eu(TTA)₃Phen in the films, which resulted in the luminescence enhancement effect. According to the proposed model of the “active enhancement circle” the distance of energy transfer from Gd-, Tb-, La-, and Y-complex to Eu-complex were calculated to be 1.2, 1.2, 0.7 and 1.0 nm, respectively.     

Luminescent Properties of a Polymer Photoluminescent Composite Containing the Binuclear (EU,TB) Complex as an Emitter

Uninuclear europium (Eu), as well as binuclear Eu and terbium (Tb), complexes were synthesized using acrylic acid (AA) as the first ligand and 1,10-phenanthroline (Phen) as the second ligand. The relative weight ratio of the europium (III) (Eu³⁺) to terbium (III) (Tb³⁺) ions of the binuclear complex was 1:1 as determined via energy dispersive X-ray analysis. The structures of the Eu(AA)₃Phen and Eu_0.5Tb_0.5(AA)₃Phen complexes were characterized by Fourier transform infrared spectroscopy. A series of tri-cellulose acetate (TCA)/ the Eu(AA)₃Phen and TCA/Eu_0.5Tb_0.5(AA)₃Phen composites were prepared by solution blending, and their luminescent properties were investigated by fluorescence spectrophotometry. The excitation spectra of all composites indicated that the TCA matrix probably affected the energy absorption and transfer of organic ligands. In TCA/Eu_0.5Tb_0.5(AA)₃Phen composites the introduced Tb³⁺ ions had some influence on energy absorption and transfer of organic ligands; the energy transfer process of the complex is suggested to be as follows: Phen→AA→Tb³⁺ion→Eu³⁺ion. The emission spectra indicated that the luminescent intensity of the TCA/Eu_0.5Tb_0.5(AA)₃Phen composites was noticeably stronger than that of the TCA/Eu(AA)₃Phen composites, suggesting that the comparatively stable and high-efficiency energy transfer process was only slightly influenced by the TCA matrix. In summary, the TCA/Eu_0.5Tb_0.5(AA)₃Phen (90/10) composite possesses fine luminescent properties for potential usage as red fluorescent materials.     

Eu~（3＋）、Tb~（3＋）与1－乙酰乙酰吲哚、1，10－邻菲啰啉二元、三元体系在溶液中荧光光谱研究

观察了以不同比例溶解在乙醇中的ＥＵ（３＋）、Ｔｂ（３＋）、１－乙酰乙酰吲哚（ＨＬ）和１，１０－邻菲啉（Ｐｈｅｎ）的荧光光谱．结果表明ＨＬ能有效地把吸收的能量传递给Ｔｂ（３＋），而不能有效地传递给Ｅｕ（３＋）．讨论了ＨＬ和Ｐｈｅｎ对Ｅｕ（３＋）、Ｔｂ（３＋）的配位作用及其对Ｅｕ（３＋）或Ｔｂ（３＋）所组成的三元体系中敏化发光性能的影响．     

Eu3+、Tb3+与1-乙酰乙酰吲哚、1,10-邻菲啰啉二元、三元体系在溶液中荧光光谱研究

观察了以不同比例溶解在乙醇中的Eu3+、Tb3+、1-乙酰乙酰吲哚(HL)和1,10-邻菲啉(Phen)的荧光光谱.结果表明HL能有效地把吸收的能量传递给Tb3+,而不能有效地传递给Eu3+.讨论了HL和Phen对Eu3+、Tb3+的配位作用及其对Eu3+或Tb3+所组成的三元体系中敏化发光性能的影响.     

2-(4-氯代苯甲酰基)苯甲酸配合物光致发光研究

以Eu3+,Tb3+为中心离子,2-(4-氯代苯甲酰基)苯甲酸(HCBBA)为第一配体,邻菲咯啉(Phen)、三苯基氧膦(TPPO)、二苯亚砜(DPSO)为第二配体,合成了多种铕铽的二元和三元配合物,并测试其荧光效能,以研究配体的加入对中心离子发光强度的影响。结果表明,合成的配合物均发出Eu(Ⅲ)和Tb(Ⅲ)的特征荧光,但相对强度明显不同。在铕与2-(4-氯代苯甲酰基)苯甲酸根(CBBA)形成的配合物体系中,Phen和DPSO显示了较强的敏化作用,且Phen敏化效果更强,而TPPO则对配合物荧光有猝灭作用。在Tb-CBBA体系中,DPSO表现出很强的敏化作用, Phen和TPPO却对配合物荧光起猝灭作用,且TPPO猝灭效果更强。经红外推测,羧酸根均以双齿桥式与Eu3+和Tb3+配位;在3 200～3 600 cm-1出现水的弱的羟基的伸缩振动吸收峰,表明配合物中含有结晶水。     

Ordered luminescent nanohybrid thin films of Eu(BA)3Phen nanoparticle in polystyrene matrix from diblock copolymer self-assembly

A simple route for fabricating highly ordered luminescent thin films based on hybrid material of diblock copolymer and europium complex, assisted with self-organization of polystyrene-block-poly(ethylene oxide) (PS-b-PEO) diblock copolymer upon solvent annealing, is presented. PS-b-PEO self-organized into hexagonal patterns and europium complex of Eu(BA)₃Phen was selectively embedded in PS blocks after solvent annealing in benzene or benzene/water vapor. During benzene annealing, the orientation of the PEO cylindrical domains strongly depended on the Eu(BA)₃Phen concentration. In contrast, when the hybrid thin films were annealed in mixture of benzene and water vapor, high degree of orientation of the PEO cylindrical domains is more easily obtained, which is independent of Eu(BA)₃Phen concentration. Furthermore, preferential interaction of PEO domains with water induces a generation of nanopores in the hybrid thin film. Atomic force microscopy (AFM), scanning electron microscopy (SEM), and transmission electron microscopy (TEM) were used to characterize the long-range lateral order and phase composition of the hybrid thin films. The ordered nanohybrid thin films kept the fluorescence property of Eu(BA)₃Phen and showed a strong red emission under the 254 nm light's irradiation. The fluorescence property was confirmed by photoluminescence (PL) spectra.