Synthesis and Complexing Properties of Three Aminopolyphosphonic Acids with Rare Earth Ions

Three white crystalline aminopolyphosphonic acids, DTHMP, TTHMP and TPHMP were synthesized by a modified Mannich reaction under gentle conditions. The products were isolated and purified with a SP-Sephadex C-25 column. The acid-base and complexing properties of three aminopolyphosphonic acids with rare earth ions were investigated by means of potentiometric titration in aqueous medium at (25 +/- 0.1) degrees C and ionic strength I = 0.1 mol/L KNO3. The successive protonation constants of ligands and the formation constants of complexes with rare earth elements were obtained. The results show a double-double effect for lgK(MHiL) against atomic number of lanthanide. The properties are advantageous for the separation of the rare earth elements.

Syntheses,Crystal Structures,and Magnetic Properties of Cobalt(Ⅱ) Complexes with 1,1-Cyclohexanediacetic Acid

Two new Co（Ⅱ） coordination polymers,{[Co_3（Hchda）_2（chda）_2（bpp）_2（H_2O）_2]}_n 1 and {[Co（chda）（bpe）（H_2O）]·3H_2O}_n 2（H_2chda = 1,1-cyclohexanediacetic acid,bpp = 1,3-bis（4-pyridinyl）propane and bpe = 1,2-bis（4-pyridinyl）ethylene）,were hydrothermally synthesized and then characterized by elemental analysis,IR spectroscopy,thermogravimetric analysis（TGA）,and single-crystal X-ray diffraction.Complex 1 possesses an infinite metal-organic layer based on triply bridged linear trinuclear subunits and complex 2 exhibits a square（4,4） grid layer with dangling lateral arms resulting from eight-membered rings above and below the layer.In addition,magnetic properties of complexes 1 and 2 are also given.

Hydrothermal Synthesis, Crystal Structure and Luminescence Properties of a New 2D Cadmium Complex Based on the 4,4'-Bis(benzimidazol-1-ylmethy1)biphenyl and Glutaric Acid Ligands

A new polymeric complex {[Cd2（bbmb）2（gt）2]＇（H2O）2}, （bbmb = 4,4＇-bis（benzimidazol-l-ylmethyl）biphenyl, H2gt = glutaric acid） has been obtained by hyclrothermal method and structurally characterized by elemental analysis, IR, XRD, TGA and single-crystal X-ray diffraction. The complex belongs to the triclinic system, space group P1 with a = 10.2417（15）, b = 13.752（2）, c = 22.201（3） A, a = 73.899（2）, β = 88.416（2）, y = 78.305（2）°, V = 2940.4（7） A3, Z = 2, C66H56Cd2N808, Mr = 1313.99, Dc = 1.484 g/cm3, F（000） = 1336 and μ = 0.787 mm-1, and features a 2D network. In the solid state at room temperature, the cadmium（Ⅱ） complex exhibits strong fluorescence absorption at 435 nm （λmax）.

Crystal Structure, Spectroscopic Characterization, and Electrochemical and Thermal Stability Properties of a Dinuclear Nickel(Ⅱ) Complex

A new nickel（Ⅱ） complex Ni2（L）2（2,2＇-bipy）2·5.5H2O with methy-bicycle[2.2.1]hept-5-ene-2,3-dicarboxylic acid（H2L） and 2,2？-bipyridine（2,2＇-bipy） as ligands has been synthesized in the mixed solvent DMF and water（v：v = 5：2）. It crystallizes in the triclinic space group P1 with a = 10.414（2）, b = 12.884（3）, c = 16.176（4） A, α = 70.715（5）, β = 80.599（5）, γ = 77.383（6）°, V = 1989.4（8） A^3, Dc = 1.531 g/cm^3, Z = 2, F（000） = 958, GOOF = 1.028, the final R = 0.0808 and w R = 0.2036. The crystal structure shows that the whole molecule consists of two independent dinuclear units, in which two nickel ions are bridged by two μ2-η1：η0 3-carboxylate groups of L2- anions. The coordination environment of Ni（Ⅱ） ion is Ni N2O3, giving a distorted square pyramidal geometry. The thermal stability and electrochemical properties of the complex were investigated.

Syntheses,Structures and Photoluminescent Properties of Cd(Ⅱ)Polymeric Complexes Based on 5-Aminoisophthalic Acid and Bipyridine Co-ligands

Two novel complexes, namely {[Cd（AIP）（4,4＇-bpy）]·1.3DMF}n（1） and [Cd（AIP）（2,2＇- bpy）]n（2）, have been synthesized through solvothermal reaction（H2AIP = 5-aminoisophthalic acid, 2,2＇-bpy = 2,2＇-bipyridine, 4,4＇-bpy = 4,4＇-bipyridine, and DMF = N,N＇-dimethylformamide） and structurally determined by single-crystal X-ray diffraction. Complex 1 shows a three-dimensional（3D） layer-pillar framework with rectangular channels, while complex 2 displays a two-dimensional（2D） wave net architecture. Furthermore, 1 and 2 were characterized by elemental analysis, infrared spectra（IR）, thermal gravimetric analyses（TGA） and fluorescence measurements. The luminescent properties of 1 dispersed in various organic solvents have been investigated systematically, demonstrating high selectivity for acetone via the fluorescence quenching effect.

Coordination Assemblies of Cd^(Ⅱ)with 5-(Ethylthio)-1H-tetrazole and Halide Ions:Synthesis,Structure,and Luminescent Properties

Three cadmium（II）-halide complexes with 5-（ethylthio）-1H-tetrazole（Hett） as ligand, namely [Cd_7Cl_2（ett）_（12）（H_2O）_2]_n（1）, [Cd_2（OH）Br（ett）_2]_n（2） and [Cd_2（OH）I（ett）_2]_n（3）, have been hydrothermally synthesized and characterized. Complex 1 was synthesized at pH = 7 and exhibits a 3D supramolecular framework, where the adjacent Cd ions form a tetrahedron unit by ett ligands bridge and the tetrahedron units share vertices to connect each other by ett bridges to form a 2D layer architecture, which is further interlinked by μ_2-Cl to form 3D structures. Complexes 2 and 3 are isostructural, generated at pH = 8.0~9.0, displaying similar 2D networks via ett ligands and different halide ions（Br-in 2, I-in 3, respectively）. In addition, thermal stabilities and luminescent properties of new complexes 1~3 have been studied.

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, Crystal Structure, and Magnetic Properties of a New Dinuclear Iron Complex with Schiff Base Ligand

A new dinuclear iron（Ill） complex has been synthesized and structurally charac- terized by X-ray crystallography： [Fem2（L）（C6HsCOO）（SO4）（CH3OH）2]·CH3CN＇CH3OH （1, H3L = N,N＇-bis（salicylidene）q,3-diamino-2-propanol）. Complex 1 belongs to orthorhombic space group Pna21 with a= 11.4400（8）, b = 22.9705（2）, c = 12.5712（9）A, V= 3303.5（4）A3, Z= 4, F（000） = 1576, Dc= 1.531 g·cm-3, Mr= 761.36,μ = 1.007 mm-1, S = 1.014, the final R= 0.0505 and wR= 0.1018. The crystal packing is stabilized by intermolecular O-H…O hydrogen bonds, forming an extended one-dimensional chain structure. The temperature dependence of magnetic susceptibility measurement shows that antiferromagnetic interaction is propagated between the metal centers. Fit as dinuclear arrangement gave parameters ofJ= 19.7 cm-1, g = 1.89 and R2 = 0.9999.

Complexation Properties and Synthesis of 1,2-Bis(2 ,2' -bipyridinyl)ethylene and 1,2-Bis(2,2' -bipyridinyl)ethane Ligands with Cu(I)

l,2-Bis(2,2'-bipyridinyl)ethylene(1) ligand was synthesized by Wittig-Horner reaction and 1, 2-Bis(2, 2'-bipyridinyl)ethane(2) ligand(which can be obtained via another route ) was prepared by hydrogenation of (1). The formation of complexes of (1) and (2) with copper (I) has been studied. The influence of the different bridge chains (CH =CH, CH2CH2) on complexation is discussed on the basis of 1H NMR spectra. Keywords Dipyridine aldehyde, Dipyridine derivative, Copper complex

Syntheses, Structure and Properties of a Strontium(Ⅱ) Complex with 5-Sulfoisophthalic Acid Monosodium

A new Sr（Ⅱ） complex, [Sr（Hsip）（H2O）] （1, NaH2sip = 5-sulfoisophthalic acid monosodium）, has been synthesized by solvothermal reaction of SrCO3 and NaH2sip at 120 ℃, and characterized by single-crystal X-ray diffraction studies, elemental analysis and FT-IR. Single- crystal X-ray diffraction reveals that compound 1 has a 3D architecture, and there is only one crystallographically independent Sr（Ⅱ） ion in 1. The coordination geometry of Sr（Ⅱ） is a distorted tetragonai anti-prism. The whole Hsip2- ligand performs aμ6-coordination model. In the solid state, complex 1 shows luminescence with the maximum emission intensity at 417 nm upon excitation at 320 nm. Thermal stability of complex 1 was also investigated.

Synthesis,Structure,and Surface Photo-electric Properties of a New Zn(Ⅱ)Coordination Complex Constructed from 2-(1H-benzotriazol-1-yl)acetic Acid and 1,10-Phenanthroline Ligands

A new binuclear Zn^Ⅱ coordination complex,Zn2（bta）（phen）2（Cl）3（1,Hbta = 2-（1Hbenzotriazol-1-yl）acetic acid and phen = 1,10-phenanthroline）,has been synthesized and characterized by single-crystal X-ray diffraction,IR spectroscopy,elemental,and photoluminescent analysis.Complex 1 crystallizes in triclinic system,space group P1 with a = 9.3040（19）,b = 10.694（2）,c =16.841（3） A°,α = 101.18（3）,β = 105.77（3）,γ = 91.72（3）°,V= 1575.8（5） A°3,C（32）H（22）Zn2Cl3N7O2,Mr =773.66,Dc = 1.631 g/cm^3,Z = 2,F（000） = 780,μ = 1.820 mm^-1,the final R = 0.1238 and wR =0.1131.X-ray diffraction analyses indicate that 1 displays two crystallographic independent Zn^Ⅱmetal centers with a distorted tetragonal pyramidal（ZnN4O） and a tetrahedral（ZnNCl3） geometries,respectively.The phen serves as a common N,N＇-bidentate ligand,and the bta^- as a unique N,O-bridged ligand in 1.In the crystal,1 forms a stable 3D supramolecular architecture by trifurcated hydrogen bonding C-H…C1 interactions and C-H…π,π…π stacking.1 showed photo-electric conversion properties.

RARE EARTH CONTAINING POLYMER TERNARY COMPLEXES AND THEIR FLUORESCENT PROPERTIES

Rare earth containing fluorescence active polymer ternary complexes were synthesized and their absorption and emission properties were investigated.

SYNTHESES AND SPECTROSCOPIC PROPERTIES OF LANTHANIDE COMPLEXES, Ln(acac)_3(Ph_3PO)_3

A series of new complexes of formula Ln(acac)_s(Ph_3PO)_3 (where Ln^(3+)=Nd^(3+), Sm^(3+), Eu^(3+), Tb^(3+), Ho^(3+)) have been prepared and characterized. The coordination of two ligands with lanthanide ions are studied by IR spectra, ~1H, ^(13)C, ^(31)P-NMR and metal-ligand charge tranafer tranaition is also discussed via electronic adaorption and luminescence spectroscopy.

SYNTHESIS AND PROPERTIES OF NEW INTERPOLYMERIC COMPLEXES

β-(2-imidazolinyl)-ethyl methyl diethoxy silane quarternary halides and its condensed polymers with bisphenol A were synthesized and characterized. The polycation-polyanion complexes were prepared by the condensed polymers and poly (styrene sulfonate). The solubility and thermal stability of interpolymeric complexes were investigated.

Crystal Structure and Luminescent Properties of[Cu(phen)_2I][Bi(phen)I_4]

The title complex, [Cu（phen）2I][Bi（phen）I4], has been successfully synthesized by a solution method. Its crystal structure was determined by X-ray diffraction method, and crystallizes in triclinic, space group P1 with a = 10.3876（2）, b = 14.4258（5）, c = 14.7128（5） ？, α = 82.569（8）, β = 73.442（7）, γ = 79.299（8）°, V = 2069.68（11）A3, Z = 2, Dc = 2.323 g/cm3, F（000） = 1318, μ（Mo Kα） = 13.132 mm–1 and T = 293（2） K. The final R = 0.0472 and w R = 0.1147 for 6027 observed reflections with I 〉 2σ（I）. In the structure of the title compound, [Bi（phen）I4]– provides us an opportunity to survey the influence of coordination component on the structure of the cation in the [Cu（phen）2I][Y] system. X-ray diffraction and luminescent spectrum study of the complex are also described.

Hydrothermal Synthesis, Crystal Structure and Surface Photo-electric Properties of a New Nickel(Ⅱ) 3-D Metalorganic Framework Constructed from the Rigid 1,4-Bis(imidazol-1-yl) benzene Ligand

A new 3-D nickel（Ⅱ） metal-organic framework（MOFs） with formula [Ni（bib）_2（SO_4）]_n（1）, where bib = 1,4-bis（imidazol-1-yl）benzene, has been synthesized and characterized by single-crystal X-ray diffraction, IR spectroscopy, elemental analysis and surface photovoltage spectroscopy（SPS）. Complex 1 crystallizes in monoclinic system, space group C2/c with a = 19.5988（6）, b = 9.7531（3）, c = 11.8146（4） ？, β = 96.185（3）°, V = 2245.20（12） ？~3, C_（24）H_（20）N_8NiO_4S, M_r = 575.25, D_c = 1.702 g/cm^3, Z = 4, F（000） = 1184, μ = 1.011 mm-1, the final R = 0.0293 and w R = 0.0702. X-ray diffraction analyses indicated that the center Ni^（2＋） ion is six-coordinated with an O_2N_4 donor set of two μ_2-SO_4^（2–） and four bib ligands, resulting in an ideal octahedral geometry. Topological analysis on complex 1 considers each Ni^（2＋） as a 6-connected node, while bib and sulfate ion as linkers, giving an α-Po topology with short Schl？fli symbol 412·63. In the crystal packing, the components interact with pairs of intermolecular C–H×××O hydrogen bonds. The SPS of 1 indicates that there are positive response bands in the range of 300~600 nm showing photo-electric conversion properties.

ClO_4^--directed Assembly of Two Co^ⅡComplexes Based on Flexible N-donor Ligands:Syntheses,Crystal Structures and Magnetic Properties

The reaction of Co^II ions with 1,4-bis（imidazol）butane（bimb） or 1,4-bis（triazol）butane（bitb） in the presence of ClO4^-, respectively affords two CoII coordination complexes, namely {[Co（bimb）3]·2ClO4}n（I） and {[Co（bitb）3]·2ClO4}n（II）. Single-crystal X-ray analysis indicates that both complexes I and II show the same α-Po topological structures. However, complex I exhibits a 2-fold interpenetrating network, while complex II features a 3-fold interpenetrating network. In addition, solid-state properties such as thermal stabilities and magnetic properties of two complexes were also investigated.

Changes in SOC and Nutrients under Intensive Tillage in Two Types of Slope Landscapes

The net effect of tillage erosion on soil properties would be associated with the spatial variation in soil constituents,and therefore plays an important role in ecological agriculture.We conducted a consecutive tillage by hoeing 15 times during a period with no rainfall in the two slope landscapes(a linear slope and complex slope) of the Yangtze Three Gorges reservoir areas,to examine the relationship between soil erosion rates and the variations in soil chemical properties and compare the effects of soil redistribution on SOC and nutrients between the linear and complex slopes.After the simulated tillage,notable changes in 137 Cs inventories of the soil occurred in the summit and toeslope positions on the linear slope,while there were significant changes in 137 Cs inventories at convex and concave positions on the complex slope.Soil profile disappeared at the summit slope boundary,with the exposure area of 16.0% and 7.6% of the experimental plot,respectively,for the linear and complex slopes due to no soil replacement.Soil organic C and nutrients were completely depleted with the disappearance of soil profiles at soil eroding zones,whereas a remarkable increase in SOC,total N and available nutrient concentrations of the post-tillage surface soil and a decrease in total nutrient concentrations(P and K) were found at depositional zones on the linear slope.For the complex slope,however,changes in SOC and nutrient concentrations of the post-tillage surface soil exhibited a patterndifferent from that on the linear slope,which showed a remarkable decrease in SOC and total nutrient concentrations but a slight increase in available nutrient concentrations after tillage in the toeslope position.Due to the gradual increase in soil depth from top to bottom of the slope,SOC and nutrient inventories in the soil profiles were significantly correlated with soil redistribution rates on both the linear and complex slopes.Tillage causes remarkable changes of soil chemical properties in the surface soil layer and soil profile,and increases SOC and nutrient inventories for the soil profile downslope in steeply sloping landscapes.

Synthesis, Crystal Structure and Fluorescent Property of a Zn(Ⅱ) Complex with 1,3-Bis(imidazol-1-yl)benzene and 1,3-Benzenedicarboxylate

A novel zinc complex [Zn（BIB）（bdc）]n（1, BIB = 1,3-bis（imidazol-1-yl）benzene, bdc = 1,3-benzenedicarboxylate） has been synthesized in solvothermal conditions. The title complex was characterized by elemental analysis, IR spectra, thermal analysis, single-crystal and powder X-ray diffraction. The result proved that the alliance of BIB and aromatic carboxylic acids is good for the diversity of getatable structure. Complex 1 crystallizes in the monoclinic system of P2/c space group with a = 11.5591（10）, b = 9.6239（8）, c = 33.727（3）A, β = 103.816（3）°, V = 3643.4（5） A^3, Z = 8, μ = 1.385 mm^-1, F（000） = 1792, Dc = 1.603 g/cm^3 and Mr = 439.72 g/mol. Additionally, luminescent properties of complex 1 are also investigated and it shows good fluorescence.