Studies on synthesis and fluorescent property of rare earth complexes RE（ABMF）2AA and copolymers RE（ABMF）2AA-co-MMA

Four new complexes RE(ABMF)2AA (RE=Sm, Eu, Tb, Dy) were synthesized by the reaction of RECl3·6H2O with acrylic acid (HAA) and 1-(2-furyl)-3-phenyl-1,3-propanedione (ABMF). The copolymerization of the rare earth complexes with methyl methacrylate was studied by using 2,2-azobis-isobutyronitrile as an initiator. The composition and structure of the four complexes were characterized by elemental analysis, UV-vis and FTIR. The glass transition temperature and molecular weight of the copolymers were determined. Photoluminescent measurement showed that ligand ABMF could efficiently transfer the energy to Sm3+ and Eu3+ ions in the complexes and sensitize the luminescence of the rare earth ions, but could not sensitize Tb3+ and Dy3+ ions. As a result, both Sm3+ and Eu3+ complexes emitted the characteristic fluorescence of Sm3+ and Eu3+ ions due to the f-f transitions. The four copolymers could emit strong fluorescence of the rare earth ions.     

铽在硫氧化镧基质中的光致发光

采用高温固相反应法制备了La2O2S∶Tb3+、La2O2S∶Tb3+,RE3+(RE=Dy,Gd,Ce,Sm)荧光粉样品并进行了相关表征。结果表明,合成样品的晶体结构与La2O2S相同,为六方晶系;荧光粉颗粒的形貌多为长方形片状;发射光谱由494 nm、545 nm、587 nm、622 nm的一系列锐发射峰组成。研究发现Tb3+的掺杂浓度对样品主发射峰545 nm的发光强度影响很大,且在摩尔分数x(Tb3+)=0.02时达到最强。稀土离子Dy3+、Gd3+对La2O2S∶Tb3+荧光粉的发光有明显的敏化作用。     

Synthesis and Characterization of Rare Earth Complexes of Ferrocenylcarbonylhydrazine

Ｔｈｅｍｅｔａｌｃｏｍｐｌｅｘｅｓｏｆｈｙｄｒａｚｉｄｅｓｈａｖｅａｔｔｒａｃｔｅｄｃｏｎｓｉｄｅｒａｂｌｅｉｎｔｅｒｅｓｔｏｗｉｎｇｔｏｔｈｅｉｒａｎｔｉｆｕｎｇａｌａｎｄａｎｔｉｂａｃｔｅｒｉａｌａｃｔｉｖｉｔｉｅｓ[1 ,2 ] .Ｔｈｅｙｃａｎａｌｓｏｂｅｕｓｅｄａｓａｎａｌｙｔｉｃａｌｒｅａｇｅｎｔｓ[3 ]ａｎｄｅｘｔｒａｃｔｉｎｇａｇｅｎｔｓｆｏｒｍｅｔａｌｓａｌｔｓ[4 ] .Ｍａｎｙｃｏｍｐｌｅｘｅｓｏｆｈｙｄｒａｚｉｄｅｓｈａｖｅｂｅｅｎｓｙｎｔｈｅｓｉｚｅｄａｎｄｃｈａｒａｃｔｅｒｉｚｅｄ[5]…     

以香豆素为配体的三元稀土配合物的合成及发光性能的研究

以香豆素为主配体,邻菲罗啉、三苯基氧化磷、氨替吡啉、水这些中性配体作为第二配体,合成了不同稀土离子(Eu3+、Tb3+、Sm3、Dy3+)的配合物,通过元素分析、红外、紫外、荧光光谱等分析,表征了这些配合物的组成结构和发光性能.结果表明,在所合成的配合物中,香豆素与铕、邻菲罗啉形成的配合物发光强度最强,对其掺入不同比例的钆,发现可改变该配合物的发光强度.     

Effect of trivalent rare earth ions doping on the fluorescence properties of electron trapping materials SrS：Eu~（2＋）

Trivalent rare-earth ions (La3+,Pr3+,Nd3+,Sm3+,Gd3+,Tb3+,Dy3+,Ho3+,Er3+,Tm3+,and Yb3+) were investigated as the codoped auxiliary sensitizer for the electron trapping materials SrS:Eu2+ in order to enhance the fluorescence properties.It was found that Sm3+ and Tb3+ had the best photoluminescence stimulated luminescence (PSL) effect among the selected trivalent rare-earth ions.All the SrS:Eu2+ samples doped by different trivalent rare-earth ions could be stimulated by 980 nm laser after being exposed to the conventional sunlight,and they emitted PSL with the peak located at 615 nm.The result also indicated that some co-doped rare earth ions could increase fluorescence intensities of the traditional electron trapping materials SrS:Eu2+.     

Study on spectroscopic properties of GdOBr:RE3+ (RE=Eu, Tb, Ce)

Rare earth ions doped gadolinium oxybromide phosphors GdOBr:RE3 (RE=Eu, Tb, Ce) were synthesized by the method of solid-state reaction at high temperature, and the VUV-VIS spectroscopic properties of the phosphors were systematically investigated. Under the excitation of VUV or UV source, the phosphors doped with Eu3 and Tb3 show a bright and sharp emission at around 620 nm corresponding to the forced electric dipole 5D0→7F2 transition of Eu3 , and at around 544 nm corresponding to the 5D4→7F5 transition of Tb3 , respectively. For GdOBr:Ce3 , a broader and intense emission spanned 370-500 nm corresponding to the d-f transition of Ce3 was observed. The excitation spectra were also analyzed.     

Synthesis, Characterization and Fluorescence Properties of Europium, Terbium Complexes with Biphenyl-4-Carboxylic Acid and o-Phenanthroline

Two series of solid complexes of europium and terbium with biphenyl 4-carboxylic acid and phen were synthesized and characterized in this report. Their elemental analysis, molar conductivities and TG-DTA studies indicate that the complexes have the composition of Eu(phen)L3·1/2H2O, Eu0.5RE0.5(phen)L3·1/2H2O; Tb(phen)L3·H2O and Tb0.5RE0.5(Phen)L3·1/2H2O. (RE=Y3 , La3 and Gd3 ; L=biphenyl 4-carboxylic acid; phen=o-Phenanthroline). The studies of their IR, UV 1H NMR and molar conductivities demonstrate that biphenyl 4-carboylic acid is bounded with RE(Ⅲ) ion. Rare earth ions coordinate with two nitrogen atoms of phen molecules directly in these rare earth complexes. The fluorescence spectra and fluorescence lifetimes of the rare earth complexes show that the fluorescent intensity and lifetime of a series of europium complexes are longer than those of the series of terbium complexes as having the some ligands. There are better fluorescent intensity and lifetime of hetero-nuclear rare earth complexes than homo-nuclear rare earth complexes for europium complexes. The fluorescence emission intensity of Eu3 is raised by inert fluorescent rare earth ions (Y3 , Gd3 and La3 ), but in Tb3 hetero-nuclear rare earth complexes the intensity of Tb3 ions are quenched by the inert fluorescent rare earth ions.     

稀土铕,铽β-二酮配合物的合成与发光性能

采用Claisen缩合反应合成了一种新型的β-二酮化合物1-(4-溴苯)-3-苯基丙烷-1,3-二酮(L),并以其为第一配体,邻菲罗啉(phen)为第二配体,合成出新型稀土铕,铽二元及三元配合物。通过元素分析、红外光谱、紫外光谱、荧光光谱对合成的配体及配合物进行了表征。元素分析确定了配合物的组成。红外光谱的分析表明第一配体L中的氧原子以及第二配体phen中的氮原子与稀土离子进行了配位。紫外光谱表明第一配体L为能量的给体,第二配体phen起协同作用。通过荧光光谱研究了配合物的发光性质,结果显示三元配合物的发光强度大于二元配合物,三元配合物Eu(L)3phen表现出Eu3+的特征发射,在593,615,653,701 nm处的发射峰分别归属于Eu3+的5D0→7Fj(j=1,2,3,4)能级间的跃迁,并且以位于615 nm处的5D0→7F2电子跃迁所发出的荧光强度最大;而铽配合物中并没有出现Tb3+的特征发射。进一步的研究表明,这是由于配体L的最低三重态能级较适合Eu3+的发射能级,配体L吸收的能量可以有效的通过Antenna效应传递给稀土中心离子,使得三元配合物Eu(L)3phen的发光强度较大。     

Energy transfer in Tb~（3＋）,Yb~（3＋） codoped Lu_2O_3 near-infrared downconversion nanophosphors

Tb3+ and Yb3+ codoped Lu2O3 nanophosphors were synthesized by the reverse-strike co-precipitation method. The obtained Lu2O3:Tb3+,Yb3+ nanophosphors were characterized by X-ray diffraction (XRD) and photoluminescence (PL) spectra. The XRD results showed that all the prepared nanophosphors could be readily indexed to pure cubic phase of Lu2O3 and indicated good crystallinity. The Tb3+→Yb3+ energy transfer mechanisms in the UV-blue region in Lu2O3 nanophosphors were investigated. The experimental results showed that the strong visible emission around 543 nm from Tb3+ (5D4→7F5) and near-infrared (NIR) emission around 973 nm from Yb3+ (2F5/2→2F7/2) of Lu2O3:Tb3+,Yb3+ nanophosphors were observed under ultraviolet light excitation, respectively. Tb3+ could be effectively excited up to its 4f75d1 state and relaxed down to the 5D4 level, from which the energy was transferred cooperatively to two neighboring Yb3+. The Yb3+ concentration dependent luminescent properties and lifetimes of both the visible and NIR emissions were also studied. The lifetime of the visible emission decreased with the increase of Yb3+ concentration, verifying the efficient energy transfer from the Tb3+ to the Yb3+. Cooperative energy transfer (CET) from Tb3+ to Yb3+ was discussed as a possible mechanism for the near-infrared emission. When doped concentrations were 1 mol.% Tb3+ and 2 mol.% Yb3+, the intensity of NIR emission was the strongest.     

Synthesis, characterization and properties of some rare earth complexes with 2,6-pyridine dicarboxylic acid and α-Picolinic acid

Five novel ternary complexes were synthesized by the rare earth with 2,6-pyridine dicarboxylic acid andα-picolinic acid.These complexes were characterized by elemental analysis,molar conductivity,FT-IR,UV-Vis,Raman,TG-DTA and XRD.The general formula of the complexes was[RE(DPA)(L α )(H2O)]·2H2O(RE=Pr 3+ ,Nd 3+ ,Sm 3+ ,Eu,Er 3+ ;DPA=2,6-pyridine dicarboxylic acid;L α =α-picolinic acid). The investigation of fluorescence properties of the Eu-complex showed that the Eu(III)ion could be sensitized efficiently by the ligand to some extent.The antibacterial activity test indicated that all the five complexes exhibited antibacterial ability against Escherichia coli and Staphylococcus aureus with broad antimicrobial spectrums.     

Study on Anticoagulation Factor I from Agkistrodon Acutus Venom by Rare Earth Ion Probes

Ｓｎａｋｅｖｅｎｏｍｓｃｏｎｔａｉｎｃｏｍｐｌｅｘｐｒｏｔｅｉｎｓｗｈｉｃｈｐｏｓｓｅｓｓｖａｒｉｏｕｓｂｉｏｌｏｇｉｃａｌａｃｔｉｖｉｔｉｅｓ ,ｉｎ ｃｌｕｄｉｎｇａｃｌａｓｓｔｈａｔａｆｆｅｃｔｓｃｏａｇｕｌａｔｉｏｎｓｙｓｔｅｍｗｉｔｈｃｏａｇｕｌａｎｔｏｒａｎｔｉｃｏａｇｕｌａｎｔａｃｔｉｖｉｔｉｅｓ .Ａｎａｎｔｉｃｏａｇｕｌａｎｔｆａｃｔｏｒ (ＡＣＦ)ｗａｓｐｒｅｖｉｏｕｓｌｙｉｓｏ ｌａｔｅｄｆｒｏｍｔｈｅｖｅｎｏｍｏｆＡｇｋｉｓｔｒｏｄｏｎａｃｕｔｕｓｆｒｏｍｓｏｕｔｈｅｒｎＡｎｈｕ…     

Stability of Rare Earth Ion-N, N′-bis（2′-Pyridine）methyl-1,10-Phenanthroline-2,9-Dimethanmine Binary Complexes

1 ,10 Phenanthrolinehasbeenextensivelyusedasanazaheterocyclicchelateligandinbothanalyticalandpreparativecoordinationchemistry[1] .Asanim portantligand ,1,10 phenanthrolineunitplaysanim portantroleforthedevelopmentofthesupramolecularchemistry .Manynovelsupramolecularcompoundsin clude 1,10 phenanthrolineunit[2～ 4 ] .Furthermore ,consideringtheuniquecombinationofchemicalstabil ities ,redoxproperties ,luminescenceemissionandex citedstatelifetime ,derivativesof 1,10 phenanthrolinehaveplayedama…     

Synthesis and fluorescence properties of Eu（Ⅲ）, Tb（Ⅲ） and Sm（Ⅲ） with β-diketone and 2,2＇- bipyridine

Three new rare earth ternary complexes,RE(PPP)3bpy(RE=Sm 3+ ,Eu 3+ ,Tb 3+ ),were synthesized by the reaction of 1-phenyl-3-(p-phenylethynylphenyl)-1,3-propanedione(HPPP)and 2,2′-bipyridine(bpy)with rare earth chloride RECl3,respectively,in alcohol solution. The compositions were characterized by means of infrared(IR)spectra,chemical analysis,elemental analysis,and thermodynamic analysis.Luminescent properties of the three complexes were studied.At room temperature,under UV light excitation,the Sm 3+ ,Eu 3+ and Tb 3+ complexes exhibited characteristic emission of the central ions.The fluorescence spectra showed that the fluorescence emission intensity of Eu 3+ complex was the strongest.The narrow strongest emission band of Eu 3+ complex was considered to be a valuable material with bright red fluorescence.     

吡嗪-2,3-羧酸-乙醇体系导数荧光法同时测定钐、铕、铽、镝

研究了各种有机溶剂对Eu^3 ,Tb^3 －吡嗪－2,3－羧酸荧光体系的增敏效应。结果发现：乙醇不仅能使Eu^3 ,Pb^3 的特征荧光增敏,而且也使Sm^3 ,Dy^3 的荧光增敏,在PH6．0,99．6％乙醇浓度体系中,Eu^3 ,Pb^3 的荧光强度分别提高44和16倍,实现了同时测定Sm^3 ,Eu^3 ,.Pb^3 ,Dy^3 四种离子,本方法已成功地应用于混合稀土氧化物中四者含量的测定。     

Properties of red-emitting phosphors Sr2MgSi2O7:Eu3+ prepared by gel-combustion method assisted by microwave

Novel red-emitting phosphors Sr2MgSi2O7:Eu3+ were prepared by gel-combustion method assisted by microwave. The phase struc-ture and luminescent properties of as-synthesized phosphors were investigated by XRD and fluorescence spectrophotometer, respectively. The results showed that the as-synthesized sample was Sr2MgSi2O7 with tetragonal crystal structure. The excitation spectrum of Sr2MgSi2O7:Eu3+ was composed of two major parts: one was the broad band between 200 and 350 nm, which belonged to the charge transfer of Eu3+-O2-; the other consisted of a series of sharp lines between 350 and 450 nm, ascribed to the f-f transition of Eu3+. The emission spec-trum consisted of two emission peaks at 593 and 616 nm, which was attributed to 5D0→7F1 and 5D0→7F2 of Eu3+, respectively. The concen-tration of Eu3+ (x) had great effect on the emission intensity of Sr2-xMgSi2O7:Eu3+x. When x varied in the range of 0.04-0.18, the intensity of emission peaks at 593 and 616 nm increased gradually with the concentration of Eu3+ increasing. It was interesting that no concentration quenching occurred. Moreover, the luminescent intensity could be greatly enhanced with incorporation of charge compensator Li+ ions.     

稀土配合物的激光诱导时间分辨荧光光谱研究

本文研究了RE(RE=DY、Eu、Sm、Tb)—HFA—TOPO—Triton X-100体系的激光诱导荧光光谱。拟定了时间分辨荧光光谱技术同时测定这四个稀土元素的分析方法,用于混合样品分析,获得了满意的结果。     

Synthesis, Characterization and Bioactivity of Complexes of Rare Earth with Bis-Schiff Base from Furoylpyrazolone

Ａｃｙｌｐｙｒａｚｏｌｏｎｅｓａｒｅβ ｄｉｋｅｔｏｎｅ ｔｙｐｅｃｈｅｌａｔ ｉｎｇｅｘｔｒａｃｔａｎｔｓ,ｗｈｉｃｈａｒｅｅｘｔｅｎｓｉｖｅｌｙｕｓｅｄｆｏｒｔｈｅｓｅｐａｒａｔｉｏｎａｎｄａｎａｌｙｓｉｓｏｆｒａｒｅｅａｒｔｈｓ.Ｔｈｅｉｒｒａｒｅｅａｒｔｈｃｏｍｐｌｅｘｅｓｍａｙｂｅｕｓｅｄａｓｌａｓｅｒｍａｔｅｒｉａｌｓ ,ｓｈｉｆｔｒｅａｇｅｎｔｓｉｎＮＭＲｓｐｅｃ ｔｒｏｓｃｏｐｙａｎｄｌｕｍｉｎｅｓｃｅｎｔｍａｔｅｒｉａｌａｎｄｈａｖｅａｔ ｔｒａｃｔｅｄｍｕｃｈａｔｔｅｎｔｉｏｎ[1 ] .…     

Enhancement of red to orange emission ratio of YPO4：Eu3＋,Ce3＋ and its dependence on Ce3＋ concentration

Eu3+ and Ce3+ co-doped YPO4 microspheres were synthesized by hydrothermal method without template. The emission spectra showed that the red emission centered at 618nm could be readily increased relatively to the orange emission centered at 590nm by controlling the doping concentration of Ce3+ ion. The investigation based on excitation spectra and decay curves demonstrated that the doped Ce3+ ions took two efficient energy transfers to Eu3+ ions and affected the lifetime of the emission states of Eu3+ ions so that the emission spectra of Eu3+ ion were accordingly tuned with the Ce3+ content increasing. This controllable red (5D0→7F2) to orange ( 5D0→7F1) emission ratio of YPO4:Eu3+,Ce3+ made it very promising for encoded anti-fake labels and bio-labels.     

Effect of electron traps on long afterglow behavior of Sr3Al2O6:Eu0.012+,Dy0.02-x3+,Hox3+

The long persistent phosphors Sr3Al2O6:Eu0.012+,Dy0.02-x3+,Hox3+ (x=0, 0.01, 0.02) were prepared by a high temperature solid state reaction. All samples showed a broad band emission peaking at ~510 nm, which could be ascribed to Eu2+ transition between 4f65d1 and 4f7 electron configurations. With the increase of substitution of Ho3+ ions for the Dy3+ ions in the as-prepared phosphors Sr3Al2O6:Eu0.012+,Dy0.02-x3+,Hox3+ (x=0, 0.01, 0.02), the initial intensity of the afterglow obviously decreased. From the thermoluminescence (TL) curves of the samples, we concluded that codoped Ho3+ ions led to a decline of the trap depth and redistribution of the trap. This may be responsible for the change of afterglow of Sr3Al2O6:Eu0.012+,Dy0.02-x3+,Hox3+ (x=0, 0.01, 0.02).     

Influence of La, Y, Gd, Cu, NH4^＋ Ions and DMSO on Luminescent Property of Terbium Complexes with Sulfosalicylate

Ｔｈｅｌａｎｔｈａｎｉｄｅｃｏｍｐｌｅｘｅｓｏｆｏｒｇａｎｉｃｌｉｇ ａｎｄｓａｓｆｌｕｏｒｅｓｃｅｎｔｍａｔｅｒｉａｌｓｈａｖｅｒｅｃｅｉｖｅｄｅｘ ｔｅｎｓｉｖｅａｔｔｅｎｔｉｏｎ .Ｔｈｅｕｓｅｏｆｆｌｕｏｒｅｓｃｅｎｔｏｒｇａｎｏ ｌａｎｔｈａｎｉｄｅｃｏｍｐｌｅｘｅｓｒｅｑｕｉｒｅｈｉｇｈｆｌｕｏ ｒｅｓｃｅｎｃｅｉｎｔｅｎｓｉｔｙａｎｄｌｏｗｃｏｓｔｃｏｍｐｌｅｘｅｓ .Ｉｎｒｅｃｅｎｔｙｅａｒｓ ,ｔｈｅｆｌｕｏｒｅｓｃｅｎｃｅｅｎｈａｎｃｅｍｅｎｔｏｆＴｂ(Ⅲ )ｏｒＥｕ(Ⅲ )ｃｏｍｐｌｅｘｅ…