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.

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.

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.

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）o, V = 4582.0（2） ?3, Dc = 1.522 g/cm3, Z = 4, μ（Mo Kα） = 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+: 5 D0 → 7 F1（594 nm） and 5 D0 → 7 F2（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.

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.

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.

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.

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.

SPECTRAL VARIATION AND CHARACTERISTICS OF LOW VALENCY RARE EARTH IONS IN COMPLEX OXIDESⅢ.EFFECT OF THE CRYSTAL ENVIRONMENT AND CHEMICAL FACTORS ON LUMINESCENCE PROPERTIES OF EUROPIUM (Ⅱ) ION

In this paper,the influence of crystal-field on the Luminescence properties of Eu^(2+) in complex oxides are studied theoretically by using purely electrostatic model,the dependence of the 4f^65d levels on Eu-O bond distance is given.Quantum chemistry calculation shows that the splitting extent of 4f^65d energy band in cubic or in octahedral fields will be inversely proportional to R^5,where R is the distance of Eu^(2+) to oxygen ligand.The value of R affects slightly the location of the centre of 4f^65d energy band.According to the exper- imental spectrum data,we have discussed the influence of the host chemical composition,the replaced sites of Eu^(2+) and degree of covalency of Eu-O bond on luminescence properties of Eu^(2+).Some regularity of fluorescence spectrum was observed. In alkali-alkaline earth-phosphates,the splitting extent of 4f^65d band (△E) becomes smaller as the Eu-O bond distance (R) increases.In Na_(3-x)(PO_4)_(1-x)(SO_4)_x and Na_(2-x)CaSi_(1-x)P_xO_4 hosts,d-d emission peak of Eu^(2+) will shift to shorter wavelength with the increase of x's value. The crystal structure data show that Eu^(2+) in K_2Mg_2(SO_4)_3 is affected more strongly by crystal-field and covalancy than in KMgF_3,so K_2Mg_2(SO_4)_3:Eu^(2+) emits blue light (E_(em)~m=400nm) and KMgF_3:Eu^(2+) produces ultraviolet fluorescence.

Synthesis and Property Studies of Transparent Resins Containing Rare Earth Complex Eu(Ⅲ) (TTA)_2(MA)_2 Phen·H_2O

A new rare earth complex Eu（III） （TTA）2（MA）2Phen · H2O was synthesized and characterized by element analysis, FTIR, UV, thermal analysis, and fluorescence spectra. The strong fluorescence and high thermal stability of Eu（III） （TTA）2（MA）2Phen · H2O were used to modify resin. The copolymer containing europium was prepared by copolymerization of Eu（III） and styrene/α- methylacrylic acid, and characterized by FTIR and fluorescence spectra. The fluorescence spectra showed that the copolymer was a sort of materials with good fluorescence property, and the higher fluorescence intensity came from the higher europium content.

对Eu(Ⅲ)配合物光转换剂光谱性质的评价

稀土配合物光转换剂无一不是Eu(Ⅲ )配合物 ,Eu(Ⅲ )配合物的荧光发射光谱与叶绿素的吸收光谱明显不能吻合 ,叶绿素对Eu(Ⅲ )配合物转换光的吸收少 ,植物光合作用对转换光的利用率低。Eu(Ⅲ )配合物光转换剂加强光合作用的功能需要重新评价。本文对稀土配合物光转换剂的研究提出建议 :进行Sm(Ⅲ )配合物光转换剂的研究 ,取代Eu(Ⅲ )配合物。

新的β-二酮及其Eu(Ⅲ)三元配合物的合成与发光研究

合成了一种新的β 二酮,4 甲氧基联苯甲酰三氟丙酮(1 (4′ meothoxybiphenyl 4yl ) 4,4,4, trifluoro butane 1,3 dione,MBPTFA),以元素分析和1H NMR谱确定了其组成;进而以MBPTFA作第一配体和邻菲罗啉(1,10 phenanthroline,Phen)为第二配体,与EuCl3反应,合成了一种三元配合,Eu(MBPTFA)3Phen。用元素分析、红外、紫外 可见吸收光谱和荧光光谱进行了表征。荧光分析结果表明:配体本身是一种良好的蓝色发光材料;配合物中的有机配体能够有效地的把吸收的能量传递给中心Eu3+离子,强烈敏化Eu3+发光,且发射谱线很窄,主发射峰为Eu3+的5D0-7F2发射。这对寻找新型稀土配合物发光材料和制备有机电郅发光器件具有一定的价值。

苯甲酸根为桥的双核Eu(Ⅲ)配合物的合成及晶体结构

在EtOH：H2O=2:1的溶剂中，以Eu（NO3）3·6H2O、C6H5COONa和Phen（邻菲哈啉）为原料，合成了四桥双核配合物［Eu2（Phen）2（C6H5COO）6］．晶体属三斜晶系，空间群P1，a=1．08156（7）nm，b=1．19331（7）nm，c=1.24401（8）nm，a=104.972（5）°，β=93．661（5）°γ=113.297（5）°，Z=1．R=0.0437．晶体中2个Eu原子处于晶体学等效位置，配位数为9，Eu-Eu间距离为0．4052nm．讨论了标题化合物的UV－Vis谱与其它Eu3+离子谱的异同．

2,5-二羟基对苯二甲酸Eu(Ⅲ)配位聚合物的合成与表征

以水/乙腈为溶剂,采用溶剂热法合成2,5-二羟基对苯二甲酸Eu(Ⅲ)配合物{[Eu_2(H_2-DHBDC)_3(H_2O)_4](H_2O)}n(其中H_2-DHBDC表示2,5-二羟基对苯二甲酸).利用X-射线单晶衍射(SCXRD)、红外光谱(FTIR)、元素分析(EA)、热重分析(TG)和荧光分光光度法(FS)等对其晶体结构和荧光性质进行分析与表征.结果表明,该晶体属于三斜晶系,P-1空间群,晶胞参数a=0.949 25(6)nm,b=1.029 9(7)nm,c=1.056 5(7)nm,α=98.164(10)°,β=111.352(10)°,γ=111.969(10)°,V=835.65(10)nm^3,Z=1.且9个氧原子在铕离子周围形成一个三帽三棱柱配位环境,Eu(Ⅲ)通过配体之间的连接形成了具有一定孔道的三维结构;荧光分析结果表明,配合物具有较好的荧光性质.

1,3-二苯基-4-酰基-5-吡唑酮Eu(Ⅲ)配合物的荧光性质

以四种 1,3 二苯基 4 酰基 5 吡唑酮 (酰基分别为苯甲酰基、苯乙酰基、丁酰基和氯乙酰基 ,化合物以DPBZP、DPPAP、DPBTP和DPCAP表示 )为配体 ,合成了Eu(Ⅲ )的二元和三元配合物。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。测定了配合物的荧光光谱 ,结果表明 :配合物发射Eu(Ⅲ )的特征荧光 ;配合物荧光强度与配体吡唑环 4 位酰基上的取代基团密切相关 ,荧光强度随配体不同的变化顺序为DPBZP >DPPAP >DPBTP >DPCAP ;第二配体邻菲罗啉具有较为明显的荧光增强作用。

碳纳米管-环糊精复合材料对Eu(Ⅲ)的吸附

在等离子体条件下用有机大分子材料环糊精对碳纳米管进行功能化处理,制备出一种新的放射性核素吸附材料,即碳纳米管-环糊精复合材料。实验研究了pH、时间、离子强度对该材料吸附Eu(Ⅲ)的影响。该材料对废水中Eu(Ⅲ)的吸附速率快,吸附率在95%以上,通过吸附方程推算得到对Eu(Ⅲ)的最大吸附量可达约80mg/g,废水中其它离子及浓度对Eu(Ⅲ)的吸附无明显影响。