Synthesis and Thermal Decomposition Kinetics of La(Ⅲ) Complex with Unsymmetrical Schiff Base Zwitterion Ligand

A new unsymmetrical solid Schiff base (LLi) was synthesized using L-lysine, o-vanillin and 2-hydroxy-l-naphthaldehyde. Solid La(Ⅲ) complex of this ligand [LaL(NO3)](NO3)·2H2O was prepared and characterized by elemental analyses, IR, UV and molar conductance. The thermal decomposition kinetics of the complex for the second stage were studied under non-isothermal condition by TG and DTG methods. The kinetic equation may be expressed as: dα/dt=A·e-E/RT·(1-α)2. The kinetic parameters(E, A), activation entropy S≠ and activation free-energy G≠ were also gained.

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 ].

独居石LA-ICP-MS U-Pb法测定北大别木子店片麻杂岩变质年龄

北大别构造带木子店片麻杂岩是目前华南陆块范围内出露的最古老岩石,但有关其变质时代和构造性质等问题仍缺乏研究。对这些岩石的变质时代开展研究,对于了解华南陆块早期地壳演化过程具有重要意义。本文利用LA-ICP-MS方法对木子店片麻杂岩中两件片麻岩样品进行了独居石的微区原位U-Pb定年和微量元素分析,采用独居石标准物质44069对年龄进行校正,独居石标准物质Trebilcock作为监控,测试结果与其推荐值在误差范围内相一致。结果显示,大多数独居石具有均一、无环带特点,且存在重稀土元素明显亏损以及负Eu异常,暗示其可能形成于变质成因。两件片麻岩样品的独居石U-Pb年龄分别为129±1Ma和130±1Ma,代表了木子店片麻杂岩发生变质作用的时间,这一年龄与木子店地区早白垩世花岗岩的侵位年龄基本一致,也与北大别造山带内大量出露的混合岩时代相吻合。研究认为大别造山带早白垩世加厚地壳的伸展垮塌和造山山根拆沉,引起了变质作用和同时代的岩浆活动,将北大别构造带从挤压向伸展的构造转换时间限定在~130Ma。

Hydrothermal Syntheses and Crystal Structures of Three Lanthanide(Ⅲ)Complexes Based on Carboxyl Derivatives of 1,10-Phenanthroline

Three lanthanide（III） complexes [Ln（4-NCP）（1,4-BDC）]n·xn H2O（Ln = Pr（1）, Sm（2）, Nd（3）. 4-HNCP = 2-（4-carboxyphenyl）imidazo（4,5-f）（1,10）phenanthroline, 1,4-H2 BDC = benzene-1,4-dicarboxylic acid） have been hydrothermally synthesized and characterized via elemental analysis, infrared spectrometry and single-crystal X-ray diffraction. Structural analyses revealed that complexes 1~3 possess similar porous three-dimensional frameworks with the point symbol {4^（12）·6~3}. Meanwhile, complexes 1~3 exhibit excellent thermal stabilities and complex 2 exhibits characteristic luminescent property.

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

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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.

Synthesis,Structure and Magnetic Properties of Novel Carboxylato-bridged Pentanuclear Copper(Ⅱ)-Lanthanoid(Ⅲ)Complexes

Six novel pentanuclear complexes [Cu 3Ln 2(ClCH 2CO 2) 12 (H 2O) 8]·2H 2O (Ln=La, Pr, Sm, Gd, Dy, or Er) were synthesized by the reaction of chloroacetic acid with Cu and Ln ions in aqueous solutions. The X ray crystallography established the structure of the Gd complex, which contains a pair of quadruply acetato bridged CuGd dinuclear subunits, and each of them is linked to the central Cu atom by a single acetato bridge. The coordination sphere of each Gd atom is completed by three aqua ligands [Gd-O=0.242 8(5)-0.244 4(4) nm] to form an 8 coordinated distorted square antiprism. The central Cu atom is coordinated by two oxygen atoms from the two bridging acetato groups and two oxygen atoms from the two monodentate acetato groups in a slightly distorted square planar fashion, while each terminal Cu atom is coordinated by the four acetato oxygen atoms at the basal plane and an aqua ligand at the apical position to form a square pyramid. The variable temperature (4 320 K) magnetic susceptibility data of the Gd complex were measured, and fitted to the Curie Weiss law with C =16.38 K cm 3·mol -1 and θ =-1.55 K, indicating very weak antiferromagnetic interaction.

Microwave assisted synthesis, spectroscopic, thermal, and antifungal studies of some lanthanide(Ⅲ) complexes with a heterocyclic bishydrazone

A bishydrazone formed by the condensation of isatinmonohydrazone and salicylaldehyde reacted with lanthanide（Ⅲ） chloride to form complexes of the type [Ln（HISA）2Cl3], where, Ln=La（Ⅲ）, Ce（Ⅲ）, Pr（Ⅲ）, Nd（Ⅲ）, Sm（Ⅲ）, Eu（Ⅲ）, or Gd（Ⅲ） and HISA= [（2-hydroxybenzaldehyde）-3-isatin]bishydrazone. Both reactions were carried out under microwave conditions. The ligand and the metal complexes were characterized on the basis of elemental analysis, molar conductance, magnetic susceptibility measurements, UV visible, infrared, far infrared, and proton NMR spectral data. The ligand acted as neutral tridentate, coordinating through the carbonyl oxygen, azomethine nitrogen, and phenolic oxygen without deprotonation. The ligand and lanthanum（Ⅲ） complex were subjected to X-ray diffraction studies. The X-ray diffraction pattern of ligand exhibited its crystalline nature and that of the lanthanum（Ⅲ） complex indicated its amorphous character. The thermal decomposition behaviour of the complex, [La（HISA）2Cl3], was examined in the temperature range of 40-800 ℃ using TG, DTG, and DTA. The ligand and the metal complexes were screened for their antifungal activities.

Preparation,Characterization and Properties of Two New Lanthanide(Ⅲ)-5-(2-pyridyl)tetrazolate Complexes

Two new mononuclear lanthanide（Ⅲ） complexes Ln（pytz）3（H2O）3·（H2O）3.5[Ln=Tb（1）;Eu（2）;Hpytz=5-（2-pyridyl）tetrazole] were synthesized by reacting Hpytz with the corresponding lanthanide（Ⅲ） ions and characterized.The single crystal X-ray diffraction analysis reveals that complexes 1 and 2 are isostructural and the lanthanide（Ⅲ） ions in both complexes 1 and 2 are nine-coordinated,with three oxygen atoms of three coordination water molecules and six nitrogen atoms of three pytz ligands,forming a monocapped square antiprism.Extensive hydrogen bonds exist,resulting in a three-dimensional supramolecular network structure by hydrogen-bonds in both complexes 1 and 2,respectively.Complex 1 exhibits typical green fluorescence of Tb（Ⅲ） ion and complex 2 red fluorescence of Eu（Ⅲ） ion,in solid state at room temperature.

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.

Degradation of Azo Dyes by Photocatalysis of Fe(Ⅲ)-oxalate Complexes/H_2O_2 in Aqueous Non-ionic Surfactant Triton X-100 Solution

Two azo dyes,C.I.Reactive Red 195(RR195)and C.I.Acid Black 234(AB234)were degraded by photocatalysis of Fe(Ⅲ)-oxalate complexes/H2O2 in aqueous non-ionic surfactant,Triton X-100(TX-100)solution.Some factors affecting the dye degradation such as TX-100 concentration,irradiation intensity,and sodium chloride were investigated.The interaction and competition between dye and TX-100 during the degradation were also examined using spectrophotometry and maximum bubble pressure method,respectively.The results indicated that TX-100 showed a significant reduction effect on degradation of two azo dyes,but which was largely confined to TX-100 concentration below the Critical Micellar Concentration(CMC).And the reduction was considerably decreased above the CMC,especially in the case of AB234.Moreover,the reducing effect of TX-100 on dye degradation almost did not vary with irradiation intensity.And the impact of sodium chloride on dye degradation was limited by the addition of TX-100.

Synthesis and Structure of a La(Ⅲ) Complex of 1,10-Phenanthroline-2,9-dicarboxylate:a Three-dimensional Network via Hydrogen Bonding Interactions

A new La（Ⅲ） complex, {[La（L）（NO3）（H2O）3]·H2O}n （L = 1,10-phenanthroline- 2,9-dicarboxylate）, has been synthesized and structurally determined by X-ray diffraction analysis. The complex crystallizes in the monoclinic system, space group P21/c with a = 7.7358（17）, b = 8.1664（18）, c = 28.271（6） A, β= 95.184（4）°, V= 1778.6（7） A3, Z = 4, C14H14LaN3O11, Mr = 539.19, Dc = 2.014 g/cm^3, μ= 2.471 mm^-1, F（000） = 1056, the final R = 0.0350 and wR = 0.0659. In this complex, each metal center adopts a ten-coordination geometry formed by two N atoms from a ligand L and eight O atoms from three H2O molecules, a nitrate ion and carboxylates of two ligands. Each ligand adopts a N2,O3-pentdentate coordination mode using two N and two O atoms chelating a La（Ⅲ）, and using another O atom of carboxylate to bridge another La（Ⅲ） center resulting in a 1D helical chain molecule. Intermolecular strong O-H…O and weak C-H…O hydrogen bonds extend the 1D chain structure into a 3D supramolecular architecture.

Photodegradation of bisphenol A in Fe(Ⅲ)-oxalate complexes solution

The aqueous photodegradation of bisphenol A （BPA） in the presence of Fe（Ⅲ）-oxalate complexes （Fe（Ⅲ）-Ox）, which are common compositions of natural water, was investigated in this study. BPA underwent rapid indirect photolysis in Fe（Ⅲ）-Ox solution under simulated solar irradiation, proceeding pseudo-first-order kinetics. The photolysis rate increased with decreasing pH or initial BPA level and increasing Fe（Ⅲ）/oxalate concentration ratio. Hydroxyl radicals （·OH）, which were generated from the photochemical processes of Fe（Ⅲ）-Ox complexes and contributed to the photooxidation of BPA, were determined by molecular probe and electron spin resonance （ESR） methods with the steady-state concentration of 2.56 × 10^-14 mol/L. Superoxide anion radical （O2^·-） was considered as the precursor of. OH and qualitatively determined by adding nitro blue tetrazolium as well as ESR experiments. Based on the structural analysis of the intermediate photoproducts of BPA in Fe（Ⅲ）-Ox complexes solution, the possible degradation pathways of BPA were proposed, involving ·OH addition, alkyl scission and alky oxidation. The results indicate that the photochemical reactivity of Fe（Ⅲ） may affect the environmental fate of BPA in natural water significantly.

Studies on some lanthanide（Ⅲ） complexes with 4-hydroxyantipyrine

Seven new lanthanide（Ⅲ） complexes with 4-hydroxyantipyrine were synthesized. These complexes were characterized by elemental analysis, molar conductance, magnetic moment measurements, FT-IR, electronic and 1HNMR spectra, X-ray powder diffraction, and thermogravimetric studies. The ligand, 4-hydroxyantipyrine （hap）, contained carbonyl oxygen and hydroxyl oxygen as potential donor sites. On coordination, deprotonation occurred and as a result, hap acted as a monobasic bidentate ligand. A coordination number 6 was assigned to the lanthanide（Ⅲ） ions in these complexes with orthorhombic structure. All the complexes were thermally stable-150℃ and underwent decomposition in three stages with the formation of Ln2O3 as the final residues.

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,Crystal Structure and Electrochemistry Properties of an Iron(Ⅲ) Complex Based on the 3,5-Pyridinedicarboxylate and Water Ligands

Reaction of 3,5-pyridine-dicarboxylic acid（3,5-PydcH2） with iron salt in hydrothermal condition results in the formation of a three-dimensional self-assembly network formulated as [C14H14Fe2N2O12]n,and it has been structurally characterized by elemental analysis,IR spectra and X-ray diffraction.It crystallizes in the monoclinic system,space group C2/c with a=9.9633（15）,b=12.0942（18）,c=7.4297（11）A and β=105.822o.The units of Fe2（pydc）2·2H2O are linked into a one-dimensional structure via the chelate carboxylate groups from the 3,5-pyridine-dicarboxylate.The interlayer hydrogen bonding interactions result in a three-dimensional supramolecular architecture.In the complex,the Fe（Ⅲ） ion displays a slightly distorted pentagonal bipyramidal geometry with seven coordination numbers.Cyclic-voltammetry measurement reveals the oxidation and reduction processes for the complex are quasi-reversible in nature.

Synthesis,Crystal Structure and Interaction with DNA of a Novel Chromium(Ⅲ) Complex Containing Salicylaldehyde Semicarbazone

The novel chromium（Ⅲ） complex with salicylaldehyde semicarbazone was synthesized and characterized by IR spectra and single-crystal X-ray diffraction analysis. The crystal belongs to the orthorhombic system, space group Pbca with a = 8.9849（13）, b = 12.0475（16）, c = 34.522（5）A, V = 3736.9（9）A3, Z = 8, C16H18C1CrN6O5, Mr= 461.81, De= 1.642 g/cm^3, F（000） = 1896,A（MoKα） = 0.799 mm^-1, the final R = 0.0370 and wR = 0.0827 for 2908 observed reflections with I 〉 2σ（I）. The interaction between the chromium（Ⅲ） complex with calf thymus DNA （Ct-DNA） has been investigated by absorption spectroscopy, fluorescence spectroscopy and viscosity measurements. The results indicated that the complex was bonded to Ct-DNA through a non-classical intercalative mode.

Synthesis, Crystal Structure and DNA-binding Property of Bismuth(Ⅲ) Complex with p-Hydroxy-phenylacetic Acid

A bismuth（Ⅲ） complex 1 （H2-4,4＇-bipy）[Bi（HPPA）5]（H2PPA）.4H2O （H2PPA = p- hydroxy- phenylacetic acid, 4,4＇-bipy = 4,4＂-bipyridyl） was hydrothermally synthesized from p-hydroxy-phenylacetic acid （H2PPA）, Bi（NO3）3＂6H20 and 4,4＇-bipyridyl, and characterized by elemental analysis, IR, molar conductivity and TG. The single-crystal X-ray diffraction studies demonstrated that the complex is of monoclinic system, space group P21 with a = 10.928（7）, b = 22.558（7）, c = 11.313（7） A, β = 91.864（4）°, V = 2787.7（4） A3, Z = 2, C58H61BiN2O22, Mr = 1347.07, F（000） = 1364, Dc= 1.605 g/cm-3, p（MoKa） = 3.247 mm-1, the final R = 0.0269 and wR = 0.0540 for 9776 observed reflections with I 〉 2or（I）. The bismuth（I/I） is seven-coordinated with O atoms, forming a monocapped octahedral geometry. Complex 1 further forms a 3D supramolecular architecture by hydrogen bonds and π-π stacking interactions. Moreover, the interaction between the complex and DNA was studied by EtBr fluoescent probe.