Eu(TTA)2(phen)(UAH)/SiR Fluorescence Materials Prepared by In-Situ Reaction Method

Eu(TTA)2(phen)(UAH) (UAH=undecylenic acid)with fine fluorescent property and active group was synthesized. The measurement and characterization of complexes were also carried out. A series of composites based silicon rubber were prepared by blending silicon rubber and Eu(TTA)2(phen)(UAH) rare earth complex with active groups. Next, the effect of vulcanizing time on the property of materials was mainly studied. The results show that the dispersed particle size of rare earth complexes decreases gradually in the vulcanizing process.     

Influence of Blending Temperature on Fluorescence Properties of Silicone Rubber Matrix Eu(TTA)2(phen)(MA) Composites

A series of fluorescent composites were prepared by blending silicone rubber with Eu(TTA)2(phen)(MA). The influence of mechanical blending temperature on fluorescent intensity of composites and dispersion of rare earth complexes in the SiR matrix were investigated. As for the cured rubber, it is found that its fluorescent intensity is relatively low compared with that of uncured rubber. Low temperature is beneficial to dispersion of Eu(TTA)2(phen)(MA) homogeneously. When the amount of rare earth complexes is low, the fluorescent intensity of composites prepared by mechanical blending method above melting point of Eu(TTA)2(phen)(MA) is much higher than that of composites prepared below melting point.     

Preparation of Eu （ TTA ）2 phen （ MA ）/SiR Fluorescent Materials under High Mechanical Blending Temperature

Eu（TTA）2（phen）（MA） complexes were synthesized, in which MA was introduced as the acidic ligand to increase the fluorescent intensity of the complexes. The complexes were characterized by scanning electron microscopy （SEM）, X-ray diffraction （XRD）, and fluorescent spectra, respectively. Different amounts of rare earth complexes were blended with silicon rubber over the melting point of Eu （TTA） 2 （phen） （MA）. Next, a definite amount of 2,5-dimethyl-2, 5-di （tert-butylperoxy） hexane was added as a cross linker to the composite, to get the uncured composites. Subsequently, the composites were vulcanized at 160℃, and silicon rubber-based composites with different contents of the complexes were prepared and their fluorescent properties were observed. The contents of rare earth complexes were 0.96 %, 2.83 %, 4.63 % and 6.36 % （mass fraction）, respectively. Moreover, the composites of Eu （TTA） 2 （phen） （ MA ）/SiR were measured by SEM, XRD, and fluorescent spectra. The measurement result shows that the fluorescent intensity of uncured rubber is similar to one of the pure rare earth complexes. However, there is no marked change of fluorescent intensity in the uncured rubber when the content of rare earth complexes continues to increase.     

Electroluminescence Based on Eu0.5 La0.5 （TTA） a phen Doped Poly N-Vinylcarbazole

A novel rare earth complex Eu_0.5La_0.5(TTA)₃phen, displaying electroluminescent property, was synthesized, and monolayer and double-layer devices were fabricated by doping it into poly N-vinylcarbazole. The characteristics of these optimized devices were investigated, and the emitting mechanism was explained through the energy band diagram. Optimized double-layer devices with a turn-on voltage of 6.5 V were achieved. At the current density of 68.48 mA·cm⁻², the maximum brightness and the current efficiency of the device reached 238.4 cd·m⁻² and 0.35 cd·A⁻¹, respectively.     

Electroluminescence Based on Eu_(0.5)La_(0.5)(TTA)_3phen Doped Poly N-Vinylcarbazole

Organic electroluminescence (OEL) has been ex-tensively studied owing to its potential application inflat panel displays ever since the first double-layerOELdevice that has high efficiency and luminescencewas fabricated in 1987[1 ~4]. When compared withcommon smaller organic molecules and polymers ,rareearth (RE) complexes exhibit extremely sharp , well-defined spectral lines due to the emissions that origi-nate fromthe lanthanide metal ions .So the electrolu-minescence (EL) of REcomplexes…     

Study on Luminescence Properties of a Novel Rare Earth Complex Eu（ TTA）2 （N-HPA） Phen

A novel rare earth complex Eu（TTA）2（N-HPA）Phen （TTA = thenoyltrifluoroacetone, N-HPA = N-phenylanthranilic acid, and phen = 1,10-phenathroline ）, which contains three different ligands, was synthesized. The Eu complex was blended with poly N-vinylcarbazole （PVK） in different weight ratios and spin coated into films. The luminescence properties of films were investigated and energy transfer between PVK and the complex was discussed. Multilayer structural devices consisting of ITO/PVK： Eu （TTA）2 （N-HPA） phen/BCP/Alq3/Al were fabricated with PVK ： Eu （TTA）2（N-HPA） as light-emitting layer. Increasing the concentration of Eu in the PVK thin film would inhibit the emission of PVK to different degrees. Finally, the pure red luminescence of europium（ Ⅲ ） was observed when the doping weight ratio was approximately 1 ： 5, which indicated an effective energy transfer from PVK to rare earth complex.     

Electrospinning preparation and luminescence properties of Eu(TTA)3phen/polystyrene composite nanofibers

Efficient luminescent composite nanofibers,composed of polystyrene(PS,Mw=250000) and europium complex Eu(TTA)3phen(TTA=2-thenoyltrifluoroacetone,phen=1,10-phenanthroline) with diameters ranging from 350 nm to 700 nm,were prepared by electrospinning and characterized by scanning electron microscope(SEM),Fourier transform infrared spectroscopy(FT-IR),fluorescence spectroscopy,and thermogravimetric analysis(TG).The room-temperature fluorescence spectra of the composite nanofibers were composed of the typical Eu3+ ion red emission,assigned to the transitions between the first excited state(5D0) and the multiplet(7F0-4).Owing to the incorporation of the europium complex into the PS fiber matrix and the subsequent distortion of the symmetry around the lanthanide ions by the capping PS,the polarization of the Eu3+ ions was enhanced,which increased the probability for electronic dipole allowed transitions.The monochromaticity(5D0→7F2/5D0→7F1) around the Eu3+ ions was also efficiently improved.Judd-Ofelt intensity parameters(Ω2 and Ω4) were determined from the emission spectra based on the 5D0→7F2 and 5D0→7F4 electronic transitions,respectively.The results showed that the Ω2 values of the composite nanofibers were apparently higher than that of the pure complex,indicating an increased covalency degree in the europium first coordination shell due to the modification of PS matrix.The modification of the polymer matrix also resulted in much higher thermal stability of the composite fibers than that of the pure complex.     

TTA-NA-Phen-Eu离子型配合物的合成及表征

以噻吩甲酰三氟丙酮(HTTA)、3-羟基2-萘甲酸(H2NA)和邻菲咯啉(Phen)为配体,合成了Na2[Eu(TTA)(NA)2(Phen)]新的离子型配合物,并用元素分析、红外光谱、紫外光谱对它进行了表征。     

Crystal and Molecular Structure of Triboluminescent Complex Eu(NO_3)(TTA)_2(TPPO)_2

Eu(NO_3)(TTA)_2(TPPO)_2 (TTA=thenoyltrifluoroacetone,TPPO=triphenylphosphine oxide),M=1212.90,triclinic P1,a=1.1081(2)nm,b=1.1857(2)nm,c=1.2580(2)nm,α=65.54(1)°,β=77.91(1)°,γ=61.99(1)°;Z=1,V=1.3281(4)nm~3,D_c=1.47g/cm~3,μ_(MoK_α)=14.1 cm~(-1).The crystal desplaystriboluminescence upon fracture.Structure study shows that the crystal is noncentrosymmetric and no disor-der is found.It is concluded that the polarity of crystals is necessary for the observation of triboluminescence.     

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.     

Syntheses and Crystal Structure of Nine-Coordinate Mononuclear Na[ EuⅢ (edta)(H2O)3] · 4H2O and Binuclear Na4[Eu2Ⅲ(Httha)2]·10H2O Complexes

The crystal and molecular structures of the Na[Eu Ⅲ (edta) ( H2 O) 3] · 4H2O ( edta = ethylenediaminetetraacetic acid) and Na4[Eu2Ⅲ (Httha)2] · 10H2 O ( ttha = triethylenetetraminehexaacetic acid) complexes were determined by single-crystal X-ray structure analyses.The crystal of Na[ EuⅢ (edta) (H2O)3] · 4H2O belongs to orthorhombic crystal system and Fdd2 space group.The crystal data are as follows: a = 1.9415 (15)nm, b = 3.544(3 )nm, c = 1.203(9)nm, V = 8.327(5)nm3, Z = 16, M = 589.27, Dc= 1.880 g· cm-3, μ= 3.108mm-1 and F(000) = 4704.The final R and wR values are 0.0312 and 0.0750 for 2091[I ＞ 2.0σ (I)] reflections, and 0.0344and 0.0766 for all 3932 unique reflections, respectively.The[EuⅢ (edta) (H2O) 3] - anion has a nine-coordinate pseudo-monocapped square antiprismatic structure in which the nine coordinate atoms, two N and seven O, are from one edta ligand and three water molecules.The crystal of Na4[Eu2Ⅲ (Httha)2] · 10H2O belongs to orthorhombic system and Pccn space group.The crystal data are as follows: a = 2.610(3)nm, b = 2.089(3)nm, c = 2.239(3)nm, V =12.208 ( 28 ) nm3, Z = 8, M = 1548.92, Dc= 1.686g·cm-3,μ = 2.115 mm-1andF(000) = 6272.Thefinal R and wR are 0.0625 and 0.1091 for 9834[I ＞ 2.0σ(I)] reflections, and 0.1608 and 0.1471 for all 37818 unique reflections, respectively.The whole complex molecule is composed of two close parts in which each one has a nine-coordinate structure with distorted monocapped square antiprismatic prism.The ttha ligand in the[Eu2Ⅲ (Httha)2] 4- anion coordinates to one Eu Ⅲ ion with three N atoms and four O atoms and to the other Eu Ⅲ ion with two O atoms.     

Synthesis and Characterization of Eu4(PMA)3(phen)0.75·7H2O Ternary Luminescent Complex

Eu(Ⅲ)-Pyromellitic acid[PMA]-1,10-phenanthroline (phen) ternary luminescent complex was prepared in ethanol and water mixed solvent. The elemental analysis, inductively coupled plasma-atomic emission spectroscopy (ICP-AES) fourier-transform infrared spectroscopy (FT-IR) indicates that its chemical constitution is Eu4(PMA)3(phen)0.75·7H2O. TG-DTA curves indicated that the complex is heat stable at the temperature of 430 ℃. The XRD patterns showed that the complex is a new crystal different from the two ligands' structures. SEM image indicates that the complex is in block shape and disperses well. Photoluminescence (PL) analysis indicates that the complex emits Eu3 characteristic luminescence under ultraviolet excitation.     

Tb(p-ABA)2(acac)phen-TDI-MDA共聚物合成及其性质

以对氨基苯甲酸、β-二酮和邻菲哆啉为配体合成了一种高荧光强度、高缩聚活性的铽配合物单体，并将铽配合物单体与TDI，MDA进行共缩聚，合成了含稀土配合物的聚脲共聚物。通过元素分析、摩尔电导、红外光谱、X射线光电子能谱和荧光光谱对配合物和共聚物的结构和性质进行了表征。结果表明：配合物具有高的荧光强度，在DMF中配合物为非电解质，铽配合物参与了共缩聚反应，共聚物的发射光谱与配合物相似，荧光强度随铽配合物含量增加而增强。采用高浓度的酸碱对键合型聚脲共聚物和直接掺杂型稀土配合物／聚脲进行长时间浸泡，结果表明键合型聚脲共聚物比直接掺杂型稀土配合物／聚脲具有更好的荧光稳定性。     

Thermochemical studies on complex of [Sm(o-NBA)_3phen]_2

A ternary complex [Sm(o-NBA)3phen]2 (o-NBA: o-Nitrobenzoate; phen: 1,10-phenanthroline) was synthesized and characterized by elemental analysis, IR, molar conductance, and thermogravimetric analysis. The dissolution enthalpies of SmCl3·6H2O(s), o-HNBA(s) and phen·H2O(s) in mixed solvent (VHCl :VDMF :VDMSO=2:2:1) were determined by calorimetry at 298.15 K. The enthalpy change of the reaction was determined to be rHmΔθ=252.49±1.60 kJ/mol. Using the relevant data in the literature and a thermochemical recycle according to Hess’s Law, the standard molar enthalpy of formation of [Sm(o-NBA)3 phen]2 (s) was estimated to be f mHΔθ=–4109.2±7.3 kJ/mol.     

铕苯丙氨酸配合物浓度对DNA分子链切断作用的影响

本文主要测定了ＤＮＡ和铕苯丙氨酸配合物〔Ｅｕ（ｐｈｅ）３（ＮＯ３）３〕在金电极上的循环伏安图，通过紫外光谱的测定初步探索了该配合物应用于ＤＮＡ分子切断剂的可能性。实验结果表明，ＤＮＡ存在时会对配合物的循环伏安曲线发生影响，而且这种影响随配合物浓度的增大而加大；紫外光谱的结果也进一步证明，配合物浓度的增大，对ＤＮＡ的切断作用越趋明显。     

Spectroscopy Study on Crystal Structure of Ce（NO3）3 （phen）2 and Interactions of Ce（NO3）3 （phen）2 with DNA

Inrecentyears ,Komiyaetal.[1] havefoundthatrareearthsionsmaybeoneofthestrongestcutre agentsofnucleicacids .Theexperimentalresults ,thatrareearthsrepresscancersonwholeanimalbodiesandonhumanbodies(invitro) ,indicatedthatrareearthselementsactuallyhavestrongf…     

Emission of Rare Earth Complex Tb0.5Eu0.5 （asprin）3phen

The coprecipitate Tho.sEuo.5(asprin)3phen was synthesized. By doping the rare earth complex into polymer PVK, the EL device was fabricated with the structure of ITO/PVK: RE/PBD/AI. Compared with the device using PVK/Eu (asprin)3phen blend as the light emitting layer, the emission of Eu^3 in the PVK/Th0.5Eu0.5(asprin)3 phen blend is great-ly enhanced along with the quenching of the emission of PVK.     

稀土配合物[REL3(4-picNO)H2O]的合成与表征

合成了2,3-二氯异丁酸根和4-甲基吡啶氮氧化物稀土三元配合物(RE=La、Ce、Pr、Nd、Sm、Eu).通过元素分析、红外、紫外、荧光、X射线粉末衍射、XPS、热分析以及摩尔电导等分析手段,确定了配合物的组成为[REL3(4-picNO)H2O](L= CH3C2H2Cl2COO -),并对它们的性质进行了讨论.     

含N_2O_2四齿希夫碱配体的稀土有机配合物的合成和表征

室温下 ,采用 Schlenk操作技术 ,用 Cp3L n和对称的希夫碱双水杨醛缩邻苯二胺 ( H2 SAL OPHEN)为原料 ,物质的量之比为 1∶ 1,在四氢呋喃介质中反应 ,合成了六个新型配合物 Cp L n SAL OPHEN( L n=Y,Pr,Sm,Ho,Er,Tm)。所有这些配合物都经过了元素分析、IR和 Ms表征     

[Eu2(p-MOBA)6(phen)2](H2O)2配合物热分解动力学研究

采用ＴＧ－ＤＴＧ技术研究了「Ｅｕ２（ｐ－ＭＯＢＡ）６（ｐｈｅｎ）２」（Ｈ２Ｏ）２（ｐ－ＭＯＢＡ代表对甲氧基苯甲酸根离子;ｐｈｅｎ表示１,１０－邻啡罗啉）在静态空气中的非温热分解过程及动力学,根据ＴＧ曲线确定了热分解过程的中单产的及最终产物,动用Ａｃｈａｒ法与Ｃｏａｔｓ－Ｒｅｄｌｆｅｒｎ法对非等温动力学数据进行分析,推断出和线步的动力学方程为ｄａ／ｄｔ＝ＡｅｘＰ（－Ｅ／ＲＴ）「－ｌｎ（１－ａ）」＾－