Synthesis and Crystal Structure of a Cobalt(Ⅱ) Coordination Polymer with Benzene-1,3,5-triacetate and 1,2-Di(pyridin-4-yl)ethene

A novel coordination polymer, [Co3（bta）2（dpe）3（H2O）2]·2H2O （1, H3bta = benzene-1,3,5-triacetic acid, and dpe = 1,2-di（pyridin-4-yl）ethene）, has been hydrothermally prepared and characterized by IR spectroscopy, elemental analysis and single-crystal X-ray diffraction. The crystal is of triclinic system, space group P , with a = 9.5687（15）, b = 11.2470（17）, c = 13.686（2） , α = 78.262（3）, β = 89.271（4）, γ = 81.292（3）°, V = 1425.2（4） 3, C60H56N6O16Co3, Mr = 1293.90, Dc = 1.508 g/cm3, F（000） = 667, μ = 0.940 mm-1 and Z = 1. The final R = 0.0707 and wR = 0.1413 for 4950 observed reflections （I 2σ（I））. In the title complex, the bta ligand acts as a four-dentate bridging ligand to link up cobalt atoms into lamellar frameworks which are further interlinked by the dpe ligands to generate a trinodal （3,4,6）-connected （4.62）2（42.68.83.102）（64.82） net.

Crystal Structure of Catena-poly-[2,2'-bisbenzimidazole Mn(Ⅱ)-μ-Benzene-1,3-dicarboxylato]

The title complex,[（BBI）Mn（BDC）]n 1（BBI = 2,2＇-bisbenzimidazole（C14H10N4）,BDC=benzene-1,3-dicarboxylate dianion（C8H10O4））,crystallizes in the monoclinic system,space group C2/c,with a=17.822（8）,b=16.181（7）,c=13.355（6）A,β=92.112（5）°,V=3848.67（304）A^3,Z=8,C22H14MnN4O4,Mr=453.31,Dc=1.565 g/cm^3,F（000）=1848,μ=0.725 mm^-1,S=1.000,the final R=0.0310 and wR=0.0589.1 contains hydrogen bonds and π-π stacking interactions between the neighboring aryl-ring of BBI＇s,which helps to form a three-dimensional crystal structure.

Investigation of Structural and Electronic Properties of [Tris(Benzene-1,2-Dithiolato)M]^3-(M = V, Cr, Mn, Fe and Co) Complexes: A Spectroscopic and Density Functional Theoretical Study

In this study, the first raw transition metals from V to Co complexes with benzene-1,2-dithiolate (L2-) ligand have been studied theoretically to elucidate the geometry, electronic structure and spectroscopic properties of the complexes. Density Functional Theory (DFT) and Time-Dependent Density Functional Theory (TD-DFT) methods have been used. The ground state geometries, binding energies, spectral properties (UV-vis), frontier molecular orbitals (FMOs) analysis, charge analysis and natural bond orbital (NBO) have been investigated. The geometrical parameters are in good agreement with the available experimental data. The metal-ligand binding energies are 1 order of magnitude larger than the physisorption energy of a benzene-1, 2-dthiolate molecule on a metallic surface. The electronic structures of the first raw transition metal series from V to Co have been elucidated by UV-vis spectroscopic using DFT calculations. In accordance with experiment the calculated electronic spectra of these tris complexes show bands at 522, 565, 559, 546 and 863 nm for V3+, Cr3+, Mn3+, Fe3+ and Co3+ respectively which are mainly attributed to ligand to metal charge transfer (LMCT) transitions. The electronic properties analysis shows that the highest occupied molecular orbital (HOMO) is mainly centered on metal coordinated sulfur atoms whereas the lowest unoccupied molecular orbital (LUMO) is mainly located on the metal surface. From calculation of intramolecular interactions and electron delocalization by natural bond orbital (NBO) analysis, the stability of the complexes was estimated. The NBO results showed significant charge transfer from sulfur to central metal ions in the complexes, as well as to the benzene. The calculated charges on metal ions are also reported at various charge schemes. The calculations show encouraging agreement with the available experimental data.

IR, 1H NMR, Electronic Properties and Conductivity Studies of N1 ,N4-Bis（Diphme）Benzene-l,4-Diamine Chloride Zirconium （IV） [{（Ar）2NC6H5N（Ar）2}ZrCl4] （Ar = C6H5）

A range of new compounds such as N1,N4-bis（diphenylmethlene）benzene-l,4-diamine zirconium （IV） chloride [{（Ar）2NC6HsN（Ar）z}ZrCl4] （Ar = C6H5） complex counting the chelating amine and chloride in position trans have been prepared. Well-defined NI,N4-bis（diphenylmethlene）benzene-l,4-diamine zirconium （IV） chloride [{（Ar）2NC6H5N（Ar）2}ZrCl4] （Ar = C6H5） was obtained by stoichiometric addition of {（Ar）2NC6H5N（Ar）2} （Ar = C6H5） and {ZrC14} in ethanol at reflex temperature. IR, 1H NMR, electronic properties using hyperchem program study has been improved for this compound such as bond distance, and this compound was also defined as electric conductivity which proves to be useful for conductively compound.

SYNTHESIS AND CRYSTAL STRUCTURE OF COMPLEX OF Er(Ⅲ) WITH BENZENE-1, 2, 4, 5-TETRACARBOXYLIC ACID

We have first synthesized [NH4]+[ErC6H2（COO）43H2O]-. 4H2O and determined its structure. The crystal is monoclinic, space group P21/n, with Z=4. Lattice parameters are: α= 10.330（4）, b=10.282（5）, c=16.446（8）（?）, β=98.75（4）°. The heavy

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.

Synthesis,Structure,Fluorescent Property and Natural Bond Orbital(NBO) Analysis of a One-dimensional Cobalt(III) Complex Containing 1,3-Benzenedicarboxylate and 2-Methyldipyrido[3,2-f:2',3'-h]quinoxaline Ligand

A novel metal-organic coordination polymer [Co（m-BDC）（Medpq）·2H2O]n（m-H2BDC = benzene-1,3-dicarboxyalic acid,Medpq = 2-methyldipyrido[3,2-f：2＇,3＇-h]quinoxaline） has been hydrothermally synthesized and structurally characterized by elemental analysis,IR spectrum and single-crystal X-ray diffraction.The title compound crystallizes in monoclinic,space group C2/c with a = 19.986（4）,b = 15.789（3）,c = 16.292（3）（A°）,β = 126.54（3）°,V = 4130.3（14）（A°）^3,C23H18N4O6Co,Mr = 505.34,Dc = 1.625 g·cm^-3,Z = 8,μ = 0.883 mm^-1,F（000） = 2072,the final R = 0.0772 and wR = 0.1428.The crystal structure of complex 1 is an infinite zigzag-like chain of hexacoordinate Co^3＋ ions,in which the Co^3＋ ions are bridged in two coordination modes by m-BDC^2＋ ligands and decorated by Medpq ligands,showing a slightly distorted octahedral geometry.Additionally,the compound shows strong fluorescence in the solid state at room temperature.Natural bond orbital（NBO） analysis is performed by using the NBO method built in Gaussian 03 Program.The calculation results show a covalent interaction between the coordinated atoms and Co^3＋ ions.

Co－fluorescence Enhancement System Based on Lanthanum（Ⅲ） for Determination of Terbium（Ⅲ）

The phenomenon of fluorescence enhancement for the system of terbium( Ⅲ ) with trimesic acid [ ben-zene-1, 3, 5-tricarboxylic acid (TMA)] in the presence of an excase of La￣(3+) in gelatin aqusous solution wasstudied. The fluorescence intensity of Tb￣Ⅲ -TMA system can be greatly increased by La￣(3+) , which causedthe largest enhancement of the fluorescence intensity over two orders of magnitude. The intermolecular transfer of energy was responsible for the mechanism of the fluorascence enhancement. Gelatin plays animportant role for the stabilization of the system. The system, having the maximum excitation and emis-sion wavelengths at 260 nm and 549 nm, respectively, shows a constant fluorescence interisity over the pHrange 4～6. The fluorescence intensity is a linear function of Tb￣(3+) concentration in the range of 8. 0 ×10 ￣(-9)～ 2. 6 × 10￣(-7) mol· L￣(-1) and the limit of detection is 2.0 × 10￣(-9) mol·L￣(-1) . The optimized procedurewas used for the determination of trace amount of terbium in rare earth oxides and international standardreference rocks with satisfactory results.

Synthesis and in vitro activities on anti-platelet aggregation of N,N'-di(2-substituted-phenyl)-4-methoxyisophthalamides and benzene- 1,3-disulfonamides

On the propose of searching for the SAR and obtaining novel antiplatelet aggregating drugs,we have described the synthesis procedure and the activities in vitro on antiplatelet aggregation of two series of derivatives,which contain both 18 N.N＇-di（2- substitutedphenyl）-4-methoxyisophthalamides（2a-2r） of the 2 series and nine N,N＇-di（2-substitutedphenyl）-4-methoxybenzene- 1,3-disulfonamides（3a-3i） of the 3 series.The results showed that three compounds 2e,2i and 3g emerged as significant activities of antiplatelet aggregation,superior to two reference drugs picotamide and aspirin,and eight compounds 2j,2k,21,2o,2p,2q,2r and 3i merely superior to picotamide.The preliminary SAR shows that it is favorable for the 2 series to increase the activities via the steric hindrance substituents attached to the two side chain benzene rings at 2-positions.And the arylamides of the 2 series have better the activity values than the arylsulfonamides of the 3 series respective except for 3b and 3g.On the contrary,electrostatic factors would not contribute evidently to the activities of the two series.The structures of 15 compounds newly synthesized have been established by MS and ~1H NMR and been first reported in this paper.

Two 3D Metal-organic Frameworks with 4-Fold [2＋2]-type Interpenetrated hms Nets Based on a Flexible Tricarboxylic Acid

Two 3D 4-fold interpenetrated metal-organic frameworks, [Mn（L）（bpy）]n （1） and [Cu（HL）（bpy）]n （2）（H3L = 4,4＇,4＇＇-（benzene-1,3,5-triyl-tri（methyleneoxy）） tribenzoic acid, bpy = 4,4′-bipyridine）, were synthesized under hydrothermal conditions, and characterized by element analyses, IR spectra, thermogravimetric analyses, X-ray powder diffraction and magnetic property studies. The single-crystal X-ray analyses revealed that 1 and 2 are homogeneous. 1 crystallizes in monoclinic, space group Cc with a = 26.794（2）, b = 11.6346（10）, c = 21.4614（18） ？, β = 91.570（2）°, V = 6687.9（10） A^3, Z = 8, Mr = 736.59, D = 1.463 g·cm^（-3）, μ = 0.458 mm^-1c, R（int） = 0.0524, F（000） = 3040, the final R = 0.0844 and wR = 0.2266 for 8092 observed reflections（I 〉 2σ（I））. 2 crystallizes in monoclinic, space group Cc with a = 27.609（12）, b = 11.126（10）, c = 21.490（9） ？, β = 92.131（2）°, V = 6597（5） A^3, Z = 8, Mr = 746.21, Dc = 1503 g·cm^（-3）, μ = 0.726 mm^-1, R（int） = 0.0542, F（000） = 3080, the final R =0.0681 and wR = 0.1831 for 6777 observed reflections（I 〉 2σ（I））. Two compounds are 3D [2＋2]-type 4-fold interpenetrated frameworks with（6^3）（6^9.8） hms topology. The magnetic study of compound 2 shows the presence of weak antiferromagnetic interaction between the Cu^Ⅱ ions in 2.

Synthesis and Structural Characterization of a New Two-Dimensional Polymeric Hybrid Material {[Cu<SUB>3</SUB>(<i>μ</i><SUB>3</SUB>-1,2,3-BTC)(<i>μ</i><SUB>2</SUB>-1,2,3-BTC)(en)<SUB>3</SUB>(OH<SUB>2</SUB>)<SUB>2</SUB>(OH)(<i>μ</i><SUB>2</SUB>-OH<SUB>2</SUB>)]<SUB>2</SUB>·5H<SUB>2</SUB>O·O}<SUB>n</SUB>

The reaction of benzene-1,2,3-tricarboxylate copper(II) trihydrate (Cu3(1,2,3-BTC)2·3H2O) and ethylenediamine (en) gave after recrystallization from methanol at room temperature violet crystalline solid of the polymeric two dimensional material {[Cu3(μ3-1,2,3-BTC)(μ2-1,2,3-BTC)(en)3(OH2)2(OH)(μ2-OH2)]2·5H2O·O}n (1) as identified by single crystal X-ray diffraction analysis. The compound was also characterized by elemental analysis, FT-IR spectroscopy, UV-vis spectroscopy, thermogravimetric analysis (TGA) and magnetic susceptibility. The molecular structure indicates crystallization in the triclinic space group P-1 with the unit cell parameters a = 12.1205(3) Å, b = 12.7026(3) Å, c = 13.9890(3) Å, α = 75.034(1)°, β = 74.957(1)°, γ = 68.415(1)°. Structural analysis also revealed that the dimeric compound is connected by Cu-O-Cu bridges and the dimer is further converted into a polymeric chain structure through bridging of one benzene-1,2,3-tricarboxylate ligand. Different coordination modes are observed at the copper atom. The Cu atom at the center is octahedral while the two other ones are pentacoordinated. Thermal analysis of the compound showed decomposition processes, while magnetic studies indicated a magnetic susceptibility μ of 3.21 BM.