Synthesis, Crystal Structure and Fluorescence Properties of a Terbium(Ⅲ) Complex with Biphenyl-2,3,3’,5’-tetracarboxylic Acid

A new terbium complex based on biphenyl-2,3,3’,5’-tetracarboxylic acid（H4bptc） has been synthesized, {[Tb（Hbptc）（H2O）4]×H2O}n（1）. Its structure was determined by single-crystal X-ray diffraction analysis and further characterized by elemental analysis, IR spectra and TG analyses. Title complex crystallizes in monoclinic, space group P21/n with a = 14.090（2）, b = 8.0824（13）, c = 15.5591（17） ?, V = 1775.4（5） ?3, Mr = 576.22, Dc = 2.156 g/cm3, μ（Mo Kα） = 4.059 mm-1, F（000） = 1128, Z = 4, the final R = 0.027 and w R = 0.0726 for 3296 observed reflections（I > 2σ（I））. Complex 1 exhibits a 2 D layer structure, and such layers are further united together into a three-dimensional supramolecular structure through π···π interaction and intricate hydrogen bonding. The fluorescence excitation and emission spectroscopy of 1 showed that H4 bptc is a kind of highly efficient sensitizer for terbium（Ⅲ） ion. The title complex also displays efficient ligand sensitized luminescence in the visible region with long lifetime of 2.02 ms in the solid state.

Stability Constants and Fluorescence of Terbium(Ⅲ) Complexes with Polyaminopolycarboxylates in Aqueous Solution

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Synthesis and the Fluorescent, Magnetic and Thermal Stability Properties of a New Terbium（Ⅲ） Complex Tb(C20H14O3N)3(C12H8N2)（H2O）·H2O

A new terbium(Ⅲ complex Tb(C20H14O3N)3(C12H8N2)（H2O）·H2O has been synthesized with 2-diphenylanine carbonyl benzoic acid and 1,10-phenanthroline as ligands. Crystal data for the complex are as follows: triclinic, space group P1, a =11.6034（6）, b = 16.2465（8）, c = 16.4427（8） ?, α = 73.168（5）o, β = 88.655（4）o, γ = 82.865（4）o, V = 2943.7（3） ?3, Dc = 1.494 g/cm3, Z = 2, μ（MoK α） = 1.272 mm-1, F（000） = 1348, the final R = 0.0535 and w R = 0.0809. The Tb（Ⅲ） ion is coordinated by nine atoms to give a monocapped square antiprism coordination geometry. The complex shows four fluorescence emission bands arising from the transitions of Tb3+: 5D4 → 7F6（491 nm）, 5D4 → 7F5（546 nm）, 5D4 → 7F4（585 nm） and 5D4→7F3（621 nm）. Also reported are the magnetic and thermal stability properties of the complex.

Synthesis, Characterization and Thermodecomposition Kinetics of Terbium(Ⅲ) Complex with Novel Schiff Base Salicylaldehyde-Taurine and 1,10-Phenanthroline

A complex of terbium(Ⅲ) with Schiff base salicylaldehyde-taurine and 1,10-phenanthroline was synthesized. The molecular formula was [Tb (sal-taurine) (1,10-phen) (NO_3)]·2H_2O (sal=salicylaldehyde, 1,10-phen=1,10-phenanthroline). The composition of the title complex was determined by elemental analysis and EDTA volumetic analysis. IR, Molar conductivity and X-ray powder diffraction were performed for its characterizations. The thermal decomposition kinetics of the complex were investigated under non-isothermal condition using the Achar differential method and the Coats-Redfern integral method. The kinetic equation for the second step corresponds to the mechanisms of the Zhuralev, Lesokin and Templman equation were obtained.

One-dimensional Supramolecular Chain Based on a Dinuclear Terbium(Ⅲ) 4-Cyanobenzoate Complex

A new dinuclear Tb（Ⅲ） 4-cyanobenzoate complex [Tb2（4-cba）6（phen）2] （4-Hcba = 4-cyanobenzoic acid and phen = 1,10-phenanthroline） 1 has been synthesized by solvothermal reaction in an ethanol/water mixed solution at 100℃ and structurally characterized by single-crystal X-ray diffraction. Crystallographic data： C72H40N10O12Tb2, Mr=1554.98, triclinic Pi, a = 9.903（3）, b = 11.769（8）, c = 15.078（8）A, a = 111.42（12）, It = 96.37（19）, γ = 101-24（14）°, V= 1572（1）A3, Z= 1, Dc = 1.642 g/cm^3, F（000） = 768 μ = 2.305 mm^-1, the final R = 0.0205 and wR = 0.0543 for 5479 reflections with I 〉 2σ（I）. Structural analysis shows that 1 displays an isolated dinuclear structure. Two eight-coordinated Tb（Ⅲ） ions are bridged by four 4-cba ligands in the syn-syn bidentate coordination mode, and two other 4-cba ligands chelate these two Tb（Ⅲ） ions. The title complex molecules are connected through π-π stacking interactions to generate a one-dimensional supramolecular chain, The characteristic infrared spectra, luminescent properties and thermogravimetric analyses have also been discussed.

Impact of Cr(Ⅲ)complexation with organic acid on its adsorption in silts and fine sands

Trivalent chromium(Cr(Ⅲ))can form stable soluble complexes with organic components,altering its adsorption properties in the water-soil environment.This increases the risk of Cr(Ⅲ)migrating to deeper soils and transforming into toxic Cr(VI)due to the presence of manganese oxides in sediments.In this study,Citric Acid(CA)was selected as a representative organic ligand to prepare and characterize Cr(III)-CA complexes.The characteristics,mechanisms and environmental factors influencing the adsorption of Cr(Ⅲ)-CA on porous media(silts and fine sands)were investigated in the study.The results show that Cr(Ⅲ)coordinates with CA at a 1:1 molar ratio,forming stable and soluble Cr(Ⅲ)-CA complexes.Compared to Cr(III)ions,the equilibrium adsorption capacity of Cr(Ⅲ)-CA is an order of magnitude lower in silts and fine sands.The adsorption of Cr(Ⅲ)-CA in silts and fine sands is dominated by chemical adsorption of monolayers,following the pseudo-second-order kinetic equation and the Langmuir isotherm adsorption model.Varying contents of clay minerals and iron-aluminum oxides prove to be the main causes of differences in adsorption capacity of Cr(Ⅲ)-CA in silts and fine sands.Changes in solution pH affect the adsorption rate and capacity of Cr(Ⅲ)-CA by altering its ionic form.The adsorption process is irreversible and only minimally influenced by ionic strength,suggesting that inner-sphere complexation serves as the dominant Cr(Ⅲ)-CA adsorption mechanism.

Synthesis, Characterization, Thermal Decomposition Mechanism and Non-Isothermal Kinetics of Salicylaldehyde Salicylhydrazone and Its Complex of Erbium(Ⅲ)

The salicylaldehyde salicylhydrazone and its complex of Er(Ⅲ) were synthesized. The formulae K·4H_2O(HL=[C_(14)H_(10)N_2O_3]^(2-), the bivalent form of the salicylaldehyde salicylhydrazone) were determined by elemental analysis and EDTA volumetric analysis. Molar conductance, IR, UV and X-ray power diffraction were carried out for the characterizations of the complex and the ligand. There are two stable five-numbered and six-numbered circles in the complex. The thermal decompositions of the ligand and the complex with the kinetic study are carried out by non-isothermal thermogravimetry. The stages of the decompositions were identified by TG-DTG curve. The non-isothermal kinetic data were analyzed by means of integral and differential methods. The possible reaction mechanism and the kinetic equation were investigated by the corresponding kinetic parameters.The activation energy value of the main step decomposition are also calculated by Kissinger′s method and Ozawa′s method.

Synthesis and Structure of a Novel Tetranuclear Erbium( Ⅲ) Complex with α-Alanine[Er_4(HAla)_6·(μ_3-OH)_4(H_2O)_8](ClO_4)_8·3H_2O

The title complex was synthesized in an aqueous solution and its crystal structure was determined by Xray diffraction. The crystal crystallizes in a triclinic system, space group P1 with a= 1.306 3(2) nm , b=1.319 4(4) nm, c=1.950 2(4) nm, α=90.597(14)°, β= 93.998(11)° , γ=94.093(13)°, V=3.344 1(12) nm3, Z=2, the final R indices are R 1= 0.065 4 , wR 2=0.126 2 respectively. The complex contains a novel tetranuclear cluster cation with four Er 3+ ions connected by four μ 3OH ions and six bridging carboxyl groups. Each erbium ion is coordinated by three μ 3OH, three carboxylic oxygen atoms from three αalanine and two oxygen atoms from water molecules, forming a squareantiprismatic coordination polyhedron.

Synthesis and Structure of a Novel Tetranuclear Erbium(Ⅲ) Complex with L-Proline(HPro)[Er_4(HPro)_4(Pro)_2·(μ_3-OH)_4(H_2O)_7](ClO_4)_6·6H_2O

The title complex was synthesized in an aqueous solution and its crystal structure was determined by Xray diffraction. The crystal crystallizes in a triclinic system, space group P1 with a= 1.306 3(2) nm , b=1.319 4(4) nm, c=1.950 2(4) nm, α=90.597(14)°, β= 93.998(11)° , γ=94.093(13)°, V=3.344 1(12) nm3, Z=2, the final R indices are R 1= 0.065 4 , wR 2=0.126 2 respectively. The complex contains a novel tetranuclear cluster cation with four Er 3+ ions connected by four μ 3OH ions and six bridging carboxyl groups. Each erbium ion is coordinated by three μ 3OH, three carboxylic oxygen atoms from three αalanine and two oxygen atoms from water molecules, forming a squareantiprismatic coordination polyhedron.

含氮杂环卡宾配体的半三明治铱(Ⅲ)配合物的合成及抗肿瘤转移作用

铱(Ⅲ)抗肿瘤配合物[(η^(5)-C_(5)MeC_(6)H_(4)C_(6)H_(5))Ir(C∧C)Cl]PF_(6)能够选择性杀伤、抑制肿瘤细胞,但其内在的作用机制尚不完全明确.采用细胞划痕法、迁移及侵袭等实验考察了金属铱(Ⅲ)配合物对A549细胞的抗转移能力,采用免疫组织化学法和蛋白印迹法分析NEDD9、β-catenin表达水平.研究结果显示:金属铱(Ⅲ)配合物对A549细胞有明显的抗转移作用,可能通过作用于NEDD9降低肺癌细胞的增殖和转移.同时该金属配合物也可通过诱发β-catenin蛋白的表达,增加细胞膜表面粘性,降低A549细胞的转移能力.

Thermal Decomposition Kinetics and Mechanism of Tb(Ⅲ) m-Methylbenzoate Complex with 1,10-Phenanthroline in Static Air Atmosphere

The thermal behavior of [Tb_2( m -MBA)_6(phen)_2](H_2O)_2( m -MBA=C_8H_7O_2, methoxybenzoate; phen=C_ 12 H_8N_2, 1,10-phenanthroline) in static air atmosphere was investigated by means of TG-DTG and DTA methods. The thermal decomposition of the title compound takes place mainly in two steps. The intermediate and the residue for each decomposition were identified by the TG curve. By the kinetic method of processing thermal analysis data put forward by Malek et al ., it is defined that the kinetics model for the first-step thermal decomposition is SB( m,n ).

Adsorption of erbium(Ⅲ) on D113-Ⅲ resin from aqueous solutions: batch and column studies

The adsorption and desorption behaviors of Er(Ⅲ) ion on D113-Ⅲ resin were investigated.Batch adsorption studies were carried out with various Er(Ⅲ) ion concentrations,pH,contact time and temperature,indicating that D113-Ⅲ resin could adsorb Er(Ⅲ) ion effectively from aqueous solution.The loading of Er(Ⅲ) ion onto D113-Ⅲ resin increased with increasing the initial concentration.The adsorption was strongly dependent on pH of the medium with enhanced adsorption as the pH turned from 3.45 to 6.75.In the batch s...

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.

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.

Intercalation Assembly, Characterization and Luminescent Properties of Novel Supramolecular Composite Materials, Tb(Ⅲ) Complex with Tetrapodal Ligand-Montmorillonite

Two kinds of Tb（ Ⅲ ） complexes with tetrapodal ligand, [TbL（NO3）]^3＋ and [TbL]^3＋ （L： 1,1, 1＇, 1＇-tera （ 2-pyridinecarboxylester ）-di （ trimethylpropane）） were intercalated into the interlayer space of montmorillonite （MT） by ion exchange and coordination reaction of L with the Tb^3＋ ion existing in the interlayer space of Tb-MT respectively. The obtained luminescent supramolecular composite materials, [ TbL （NO3） ]^2＋-MT and [TbL]^3＋-MT were characterized by elemental analysis, XRD, FT-IR, UV-vis and thermal analysis. At the same time, the luminescent properties of the materials were also studied. The results show that the intercalated materials with regular layered structure, good thermal stability and the interlayer spacing （d001） approximates to the size of the complex ions which are located in the interlayer space of MT in the form of a monolayer.

Investigation on Molecular and Crystal Structures of Metal Complexes with Aminopolycarboxylic Acids——Synthesis and Structure of K[In~Ⅲ(EDTA)(H_2O)]·2H_2O

The title complex was synthesised and its molecular and crystal structures were determined by single crystal X ray reflection structure analysis. The crystal data are as follows: K[In Ⅲ(EDTA)(H 2O)]·2H 2O (EDTA=ethylene diamine N, N, N′, N′ tetraacetate), Monoclinic, C c space group, a=0.9096(2) nm,b=1.1996(2) nm, c =1.5144(3) nm, β =99.40(3)°, V =1.6302(6) 3, Z =3, D c=1.498 g·cm -3 , μ =1.325 mm -1 , F (000)=726, R =0.0320 and R W=0.0903 for 2315 observed independent reflections. The complex anion [In Ⅲ(EDTA)(H 2O)] - has a seven coordinate pseudo pentagonal bipyramidal (PB D 5h ) structure, in which the EDTA serves as a hexadentate ligand with two N atoms and four O atoms and one water molecule (H 2O) directly coordinated to the central metal ion In Ⅲ as a seventh ligand. 〓〓

Synthesis and Characterization of Some Lanthanide(Ⅲ) Complexes with 4-[N-(2-methoxybenzylimine)formyl]-2, 3-dimethyl-1-phenyl-3-pyazolin-5-one

A series of seven novel lanthanide（Ⅲ ） nitrato complexes with 4-[ N-（2-methoxybenzylimine）formyl] 1-2, 3- dimethyl-1-phenyl-3-pyazolin-5-one （2mbfa）, were synthesized. These complexes were characterized by elemental analysis, molecular mass determination, conductance and magnetic moment measurements, IR, UV-visible, and ^13CNMR spectral studies, In these complexes, the Schiff base, 2mbfa, acts as neutral bidentate ligand by utilizing the carbonyl oxygen and azomethine nitrogen as donor sites. All the three nitrate ions are also coordinated unidentately with 7 coordination for the lanthanide（Ⅲ） ions with a tentative monocapped octahedral geometry for the complexes. All the seven lanthanide（Ⅲ） complexes have a general formula, [ Ln（2mbfa）：（NO3）3 ].

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）.

Syntheses and Magnetic Properties of Cu（Ⅱ）－RE（Ⅲ） Heterobinuclear Complexes with N，N′－Bis（3－carboxyisalicylidene）－trimethylenediamine

ine heterobinuclear complexes of Cu (Ⅱ)-RE (Ⅲ) with N, N′-bis-(3-car-boxylsalicylidene ) trimetliylenediamine (TS) were syntliesized and characterized bymeans of elemental analyses, molar conductivity, thermogravimetry,IR and elec-tronic spectra. The measurements of variable-temperature magnetic susceptibilitysliow that there exists only a very weak antiferromagnetic spin exchange interactionbetween the ions of Cut(Ⅱ) and RE(Ⅲ) in CuRETSCI . 3H_2O.

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.