Eu(Ⅲ) complexes involving 1,3,5-triazine diphosphine oxides

The 1,3,5-triazine diphosphine oxide ligands with donor-acceptor properties formed strong complexes with europium（Ⅲ） ion in acetonitrile. Spectrophotometric titrations and mass spectra indicated that two ligands coordinated to one europium ion. The stability constants varied from 11.64 to 14.60 （log 13）. Binary complexes exhibited rather weak luminescence in solution. 1,3,5-triazine diphosphine oxides engaged as co-ligands in Eu（Ⅲ） （2-thenoyltrifluoroacetonate）3 complex contributed to the overall photoluminescence and allowed for excitation with longer wavelengths than the parent complex.

Preparation and spectroscopic, and thermal decomposition kinetic studies of europium(Ⅲ) complex [Eu(HNBD)_3] (HNBD: 1-(6-hydroxy-1-naphthyl)-1,3-butanedione)

The complex of Eu（IH） with 1-（6-hydroxy- 1-naphthyl）- 1,3-butanedione （HNBD） was prepared for the first time and characterized by elemental analysis, IR, UV, fluorescence spectrum, and DTA-TG-DTG techniques. The IR and UV-visible spectra showed that Eu（Ⅲ） ion was coordinated to the HNBD ligand. The fluorescence spectrum showed the presence of Eu^3＋ characteristic emission. The TG-DTA-DTG curves showed that the thermal decomposition of the anhydrous complex was a two-stage process and the final residue was Eu2O3. The thermal decomposition kinetic parameters of the complex were evaluated from TG-DTG data by using three kinds of integral methods （Coat-Redfem equation, Horowitz and Metzger equation, Madhusudanan-Krishnan-Ninan equation）. The kinetic parameters of the first stage are E^＊ = 164.02 kJ.moll, A = 1.31 × 10^15 s^-l, AS^＊= 42.27 J·K^-l·mol^-l, △H^＊ = 159.51 kJ·mol^-l, △G^＊= 136.54 kJ·mol^-l, and n = 3.1, those of the second stage are E^＊= 128.52 kJ·mol^-l, A = 1.44× 106 s^-1, △S^＊= - 136.89 J·K^-l·mol^-l, △H^＊ = 120.41 kJ·mol^-l, △G^＊= 283.85 kJ·mol^-l, and n = 1.1.

Eu(Ibu)_(3)phen配合物的合成表征及发光性

以药物布洛芬为第一配体,稀土离子Eu(Ⅲ)为中心离子,采用溶剂法合成了Eu^(3+)、布洛芬(Ibu)和邻菲罗啉(phen)的稀土-布洛芬药物配合物Eu(Ibu)3phen,采用元素分析、紫外光谱、红外光谱对配合物进行了初步结构表征,并研究了配合物的荧光性能.结果表明,该合成方法简单,Eu(Ibu)_(3)phen产率较高,配合物Eu(Ibu)_(3)phen的荧光发射光谱在612 nm出现Eu离子强特征荧光发射峰.该配合物有较好的发光性能,可作为安全环保的荧光材料.

Eu掺杂ZnO多孔片状材料的制备及其降解印刷染料RhB

采用常温络合-水解法构筑Eu掺杂Zn O多孔片状材料。通过SEM、TEM、XRD、EDS等表征手段证明稀土元素Eu成功掺杂到Zn O之中,Eu-Zn O的形貌为多孔片状结构。研究了Eu-Zn O多孔片状材料对染料的光催化性能。结果表明:该材料对Rh B具有较好的降解效率,降解效率高达99.2%,循环稳定性能高达98.3%,远大于商用Zn O的76.2%的降解效率和82.3%的循环稳定性能,由以上数据说明Eu-Zn O具有很好的光催化降解效率和循环稳定性能。其优异的光催化性能归因于稀土元素Eu掺杂和多孔片状结构。

Synthesis of Eu(Ⅲ) and Tb(Ⅲ) Complexes with New Aryl Amide Type Tetrapodal Ligand and Their Luminescence Properties

A new aryl amide type tetrapodal ligand L (1, 1, 1, 1 tetrakis-{[(2 benzylaminoformyl) phenoxyl]methyl}methane) and its europium and terbium nitrate complexes were synthesized. The luminescence properties of these complexes were also studied.

一例Eu-MOF材料的构筑及对Fe^(3+)与硝基芳香族爆炸物的荧光检测性能

金属阳离子和硝基芳香族爆炸物的大量排放对环境和人体健康造成了严重威胁,对它们的高效检测具有重要的研究意义和挑战性,金属-有机骨架(MOFs)是一类新型的荧光传感检测材料.本文采用溶剂热法合成了一例具有fcu拓扑结构的Eu-MOF材料,[(CH_(3))_(2)NH_(2)]_(2)[Eu_(6)(μ_(3)-OH)_(8)(EDDC)_(6)]·8DMA·3MeOH·6H_(2)O[JLUMOF128,H_(2)EDDC=(E)-4,4′-(乙烯-1,2-取代基)二苯甲酸],并通过单晶X射线衍射、粉末X射线衍射、X射线光电子能谱、红外光谱、元素分析和热重分析对其结构及组成进行了表征.结果表明,由于荧光配体H_(2)EDDC的引入,JLU-MOF128表现出显著的荧光性能,在DMF溶液中对Fe^(3+)、2,4,6-三硝基苯酚(TNP)和2,4-二硝基苯酚(2,4-DNP)具有较好的检测效果,Ksv值分别为2.09×10^(4),8.49×10^(4)和5.75×10^(4)L/mol,检测限分别为5.99,1.51和1.93μmol/L.在金属阳离子和硝基芳香族爆炸物的检测方面,JLU-MOF128是一种理想的多感应荧光传感材料.

Synthesis,Fluorescence and Magnetic Properties of a New Europium(Ⅲ)Complex Eu(C14H9O3)2(C12H8N2)2(NO3)

A new europium(III)complex Eu(CHO)(CHN)(NO)has been synthesized with 2-benzoylbenzoic acid and 1,10-phenanthroline as ligands.Crystal data for the complex are as follows:monoclinic,space group P2/c,a=9.6733(6),b=22.9521(14),c=19.7701(12)?,β=94.9800(10)o,V=4372.8(5)?~3,D=1.557 g/cm~3,Z=4,μ(Mo Kα)=1.501 mm,F(000)=2064,the final R=0.0214 and w R=0.0510.The Eu(III)ion is coordinated by ten atoms to give a bicapped square antiprism coordination geometry.The complex shows two intense fluorescence emission bands arising from the transitions of Eu:~5D→~7F(594 nm)and ~5D→~7F(618 nm).In addition,its XT decreases from 1.29767 cm~3?mol?K at 300 K to 0.01531 cm~3?mol?K at 2 K.

Eu(Ⅲ)功能化金属-有机框架的合成及其对1-萘酚的荧光传感

采用溶剂热合成方法,合成了一例金属-有机框架{[Zn_(2)(OH)(TZI)·2H_(2)O]·6DMF}n(1)(TZI为5-四氮唑间苯二甲酸),并利用单晶X射线衍射、元素分析、红外光谱、热重分析、粉末X射线衍射等手段对化合物进行了结构表征。单晶X射线衍射结果显示配合物1呈现出三维孔道结构,并且孔道中存在未配位的羧基和配位的水分子。随后通过后合成法将Eu(Ⅲ)离子引入到框架中得到具有红光发射特征的Eu(Ⅲ)@1。在275 nm的激发光下,Eu(Ⅲ)@1存在两组荧光发射,第一组在418 nm处的宽峰为配合物1的荧光发射,荧光源于有机配体的吸收和发射;第二组五个发射峰为Eu(Ⅲ)离子的红色特征发射峰,其主峰为619 nm。尿液中其他成分抗干扰性实验结果表明,Eu(Ⅲ)@1荧光探针对于生物标记物1-萘酚非常敏感,能够导致红色荧光猝灭(619 nm),并伴有青色荧光增强(465 nm),对1-萘酚具有高选择性。荧光滴定实验结果显示Eu(Ⅲ)@1基于465和619 nm处荧光发射峰对1-萘酚的检测限分别为6.95μmol/L和1.75 mmol/L。

Crystal Structure and Fluorescent Study of a Binuclear Europium(Ⅲ) Complex

A novel binuclear Eu（Ⅲ） complex [Eu2（dpa dioxide）2（NO3）4（bpdioxide）-（EtOH）] （dpa dioxide = di-2-pyridylamine N,N＇-dioxide, bpdioxide = 2,2＇-bipyridine N,N＇-dioxide） has been synthesized and it exhibits strong and sharp fluorescent emission at 614 nm under UV radiation of 245 nm at room temperature. X-ray structural determination indicates two independent Eu（Ⅲ） ions in the structure with different EuO8N and EuOgN environments. The compound crystallizes in the triclinic system, space group P1, with a = 10.8089（7）, b = 11.4670（8）, c = 17.1440（12） A, α = 92.834（2）, β = 93.854（3）, γ = 95.433（2）°, Z = 2, Dc = 1.876 g/cm3, V= 2107.3（2） A3, F（000） = 1168.0, the final R = 0.032 and wR = 0.086 for 6331 observed reflections with I 〉 2σ（I）.

Synthesis and Fluorescent, Magnetic and Thermal Stability Properties of a New Europium（Ⅲ） Complex Eu2(C15H11O3)6(C12H8N2)2

A new europium(III)complex Eu2(C15H11O3)6(C12H8N2)2 has been synthesized with 2-(4-Methylbenzoyl)benzoic acid and 1,10-phenanthroline as ligands.Crystal data for the complex are as follows:monoclinic,space group P21/n,a=15.1238(5),b=13.5928(4),c=22.9840(7)?,β=104.132(3) ,V=4582.0(2)?3,Dc=1.522 g/cm3,Z=4,μ(MoKα)=1.433 mm-1,F(000)=2128,the final R=0.0447 and wR=0.0826.The Eu(III)ion is coordinated by eight atoms to give a distorted square antiprism coordination geometry.The complex shows two intense fluorescence emission bands arising from the transitions of Eu3+:5D0→7F1(594 nm)and 5D0→7F2(617 nm).The complex is an antiferromagnetism system in the range of 150~300 K.Also reported in the paper is the thermal stability property of the title complex.

Fe(Ⅲ)-XG配合物选择性絮凝微细粒赤铁矿与石英及其机理研究

基于金属离子配位理论,将FeCl_(3)·6H_(2)O与黄原胶(XG)按一定比例混合制备Fe(Ⅲ)-XG配合物,用于改善微细粒赤铁矿难沉降、回收效果差的问题。采用沉降实验研究了不同条件下Fe(Ⅲ)-XG对微细粒赤铁矿和石英的选择性絮凝行为,结合动电位、红外光谱和显微镜分析,揭示Fe(Ⅲ)-XG对赤铁矿的絮凝作用机理。矿物絮凝沉降试验结果表明:以黄原胶和Fe(Ⅲ)为絮凝剂,无法实现赤铁矿与石英的选择性絮凝,而黄原胶与FeCl_(3)·6H_(2)O质量比为1︰9时生成的Fe(Ⅲ)-XG配位絮凝剂,对赤铁矿和石英表现出较强的选择性絮凝作用,pH值为6时两者沉降率差异最大,分别为91.50%和39.96%。显微镜观察结果证实,Fe(Ⅲ)-XG作用下,赤铁矿颗粒形成块状絮体,且絮体密实程度更大,而石英颗粒间未发生团聚作用,处于相对分散的状态。Zeta电位、溶液化学计算、吸附量实验与红外光谱分析结果表明:黄原胶主要通过羧酸基团的羰基C=O与Fe^(3+)发生配位作用形成Fe(Ⅲ)-XG配合物,Fe(Ⅲ)-XG在石英和赤铁矿表面吸附方式不同,因而在两种矿物表面吸附量不同。Fe(Ⅲ)-XG中的羟基氧和赤铁矿表面的铁元素发生化学键合特异性吸附在赤铁矿表面,而在石英表面只有微弱的氢键吸附。通过FeCl_(3)·6H_(2)O与黄原胶配位组装可显著提升微细粒赤铁矿选择性絮凝分离效果,为赤铁矿选择性絮凝分选提供新的策略和理论指导。

Synthesis,Fluorescence and Magnetic Properties of a New Europium(Ⅲ) Complex Eu(L)3(Phen)2

A new europium（III） complex Eu（L）3（Phen）2（1） with 2-benzoylbenzoic acid（HL） and 1,10-phenanthroline（Phen） as ligands has been synthesized. Crystal data for the complex are as follows： monoclinic, space group P21/c, a = 2.2577（4）, b = 1.23484（19）, c = 1.8789（3） nm, β = 94.918（3）o, V = 5.2189（14） nm^3, Dc = 1.512 g/cm^3, Z = 4, μ（Mo Kα） = 1.269 mm^-1, F（000） = 2408, the final R = 0.0433 and w R = 0.1038. The Eu（III） ion is coordinated by nine atoms to give a single-capped square antiprism coordination geometry. 1 shows two intense fluorescence emission bands arising from the transitions of Eu^3＋： ^5D0→^7F1（597 nm） and ^5D0→^7F2（615 nm） with an excitation wavelength of 396 nm. In addition, 1 displays antiferromagnetic property at low temperature.

Synthesis,Characterization,Optical Property and Bioactivity of the Eu(Ⅲ)Complex with Aromatic Carboxylic Triazole

A novel complex{[Eu（H;TIA）(C;O;);（H;O）;]·H;O};of Eu（Ⅲ）with aromatic carboxylic triazole(H;TIA=5-（4H-1,2,4-triazol-4-yl）isophthalic acid,H;C;O;=oxalic acid)was hydrothermally synthesized and characterized by IR,UV-Vis,emission spectra and optical activity,and its crystal structure was determined.It crystallizes in triclinic system,space group P1 with a=7.4452（13）,b=10.776（2）,c=11.286（2）?,α=110.546（3）°,β=106.604（3）°,γ=99.031（3）°,V=486.0,GOOF=1.096,the final R=0.0196 and w R=0.0527 for 3081 observed reflections with I≥2σ（I）,R=0.0209 and wR=0.0535 for all data with（Δ/σ）;=0.001,（Δρ）;=0.48 and（Δρ）;=–0.46 e·?;.The natural bond orbital（NBO）charges,electrostatic potential（ESP）and frontier orbital of this complex were also analyzed.The results of anti-bacterial activity against Gram positive（S. aureus）and Gram negative（E. coli）bacteria reveal that the studied complex possesses a moderate inhibiting effect,and the inhibition effect on E.coli is better.

A new liquid membrane diffusion model for characterizing the adsorption kinetics of europium by using a continuous measurement of adsorption platform

To explore the kinetic adsorption under continuous and nonequilibrium states, an integration of continuous measurement and adsorption platform kinetics method was proposed, which was initially called the ICM-AP kinetics method, and a corresponding kinetic adsorption experimental method was developed. Adsorption experiments of europium(Eu) on Ca-bentonite,Na-bentonite, and the D231 cation exchange resin were performed using the ICM-AP kinetics method and continuous measurements. Because the kinetic experimental results observed in this study were different from those of traditional batch adsorption data, pseudo-first-order or pseudo-second-order kinetic models were unsuitable for fitting the experimental data.Hence, a liquid membrane diffusion(LMD) model was developed based on the assumption of simultaneous adsorption/desorption to discuss the mechanism of kinetic adsorption. The kinetic adsorption mechanism was also studied by using XPS.The results indicated that the proposed adsorption model can fit the experimental data more suitably, and the adsorption/desorption behaviors of Eu on bentonite and the D231 resin were simultaneously observed, suggesting that the adsorption kinetics of Eu(Ⅲ) was mainly dominated by hydrated Eu(Ⅲ) ions on the liquid membrane.

Syntheses and Structural Studies of Nine-Coordinate Mononuclear K[Eu~Ⅲ(edta)(H_2O)_3]·3.5H_2O and Binuclear K_4[Eu~~Ⅲ__2(Httha)_2]·13.5H_2O Complexes

The crystal and molecular structures of K[Eu~Ⅲ(edta)(H_2O)_3]·3.5H_2O (H_4 edta=ethylenediaminetetraacetic acid) and K_4[Eu~~Ⅲ__2(Httha)_2]·13.5H_2O (H_6 ttha=triethylenetetraminehexaacetic acid) complexes were determined by single-crystal X-ray structure analyses. The crystal of K[Eu~Ⅲ(edta)(H_2O)_3]·3.5H_2O complex belongs to orthorhombic crystal system and Fdd2 space group. The crystal data are as follows: a=1.9849(6)nm, b=3.5598(11)nm, c=1.2222(4)nm, V=8.636(5)nm^3, Z=16, M=596.37, D_c=1.835 g·cm^(-3), μ=3.166 mm^(-1) and F(000)=4752. The final R and wR values are 0.0269 and 0.0692 for 2936 [I>2.0σ(I)] reflections, and 0.0317 and 0.0708 for all 7284 unique reflections, respectively. The [Eu~Ⅲ(edta)(H_2O)_3]-complex 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 the K_4[Eu~Ⅲ_2(Httha)_2]·13.5H_2O complex belongs to monoclinic system and P2(1)/n space group. The crystal data are as follows: a=1.1337(3) nm, b=2.5753(6) nm, c=2.2138(6) nm, β=102.871(5)°, V=6.301(3) nm^3, Z=4, M=1682.33, D_c=1.773 g·cm^(-3), μ=2.339 mm^(-1) and F(000)=3404. The final R and wR are 0.0514 and 0.0906 for 11144 [I>2.0σ(I)] reflections, and 0.0976 and 0.1068 for all 26048 unique reflections, respectively. The complex molecule is composed of two close parts in structure. Every part around the Eu~Ⅲ ion in the [Eu~~Ⅲ__2(Httha)_2]^(4-) complex anion has a nine-coordinate structure with distorted monocapped square antiprismatic prism, in which the ttha ligand coordinates to one central Eu~Ⅲ ion with three N atoms and four O atoms and to the other Eu~Ⅲ ion with two O atoms.

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.

STUDIES ON THE VOLTAMMETRIC BEHAVIOR OF EU(Ⅲ)-ALDOPENTOSE AND EU(Ⅲ)-D-RIBOSE-L-AMINO ACIDS COMPLEXES

The rate of voltammetric reduction of Eu(Ⅲ)in acetate solution was increased by the formation of a complex with ribose,lyxose or arabinose.If a ternary complex of Eu(Ⅲ)-D-ribose-L-phenylanaline formed on the surface of mercury electrode,the redox process of Eu(Ⅲ)became more reversible than that of Eu(Ⅲ)-D-ribose in solution phase.

羟胺强化Fe(Ⅲ)-NTA络合物活化过二硫酸盐降解磺胺甲恶唑

针对Fe(Ⅱ)/过二硫酸盐(Peroxydisulfate,PDS)高级氧化技术存在的pH值应用范围窄、铁泥产量大等缺陷,研究构建Fe(Ⅲ)-氨三乙酸(Nitrilotriacetic Acid,NTA)/羟胺(Hydroxylamine,HAm)/PDS体系,以在中性条件下高效降解水中新污染物磺胺甲恶唑(Sulfamethoxazole,SMX)。研究结果显示,Fe(Ⅲ)-NTA/HAm/PDS体系在pH=7条件下对SMX的降解率可达91%,该体系降解SMX的主要活性物种为·SO_(4)^(-)和·OH。SMX在Fe(Ⅲ)-NTA/HAm/PDS体系中的降解效率随溶液pH值的升高而降低,且增加Fe(Ⅲ)、PDS的用量会加速SMX降解。NTA的引入可将Fe(Ⅱ)/PDS体系的pH值应用范围由酸性拓展至弱碱性,与此同时,向体系内加入HAm可有效减少铁泥的产量。根据检测到的降解产物,提出SMX在Fe(Ⅲ)-NTA/HAm/PDS体系中可能的降解途径包括断键反应、羟基化反应、氨基氧化反应。双酚AF、双氯芬酸、土霉素等其他新污染物也能在Fe(Ⅲ)-NTA/HAm/PDS体系中被高效去除,表明该体系在新污染物的降解领域有较大的应用潜力。

ENERGY TRANSFER FROM PHTHALIC ACID-TERBIUM COMPLEX TO EUROPIUM(Ⅲ)

The intramolecular energy transfer of ortho-phthalic acid-terbium[Tb(phth)_3]and ortho-toluic acid-terbium[Tb(tolu)_3],the intermolecular energy transfer from Tb(phth)_3 to Eu^(3+) in solution and their luminescent property have been studied by absorption,Infrared,fluorescence and time-resolved emission spectroscopic method.The influences of solvents and pH of the media on the emission intensity and the lifetime are discussed as well.

Fe(Ⅲ)/2,6-吡啶二羧酸活化高碘酸盐强化染料脱色的效能与机制

有色染料是环境中非常重要的污染源之一,严重威胁着水生生态环境和人类健康。由于其难以被天然降解,且传统的污水处理工艺亦无法实现其高效去除,因此急需开发绿色、高效的水处理工艺进行有色染料污染控制。发现Fe(Ⅲ)/2,6-吡啶二羧酸(2,6-PDA)可高效活化高碘酸盐(PI)实现亚甲基蓝(MB)这一典型染料的高效降解。实验结果表明,该体系在Fe(Ⅲ)浓度为10μmol/L、2,6-PDA浓度为10μmol/L和PI浓度为200μmol/L时,可在pH 3.0条件下使5 mg/L MB降解率在120 s内大于97%。该方法依托高级氧化原理和配位强化策略,利用PI对有色染料进行降解,为目前染料废水治理提供了新思路从而有效地修复了污染水体。