柔性二羧酸铜配合物的合成与晶体结构

通过液相扩散法合成了一个新的配位聚合物Cu(CBA) PY2 (H2O)(CBA为4-(3('-)羧丙酰胺基)苯甲酸阴离子,Py为吡啶),并对该化合物进行了元素分析、红外、热重、粉末X射线衍射表征,其结构由X射线单晶衍射确定.该化合物属于单斜晶系,空间群P2/c,晶胞参数:C21 H21CuN3O6,a=2.15208(12) nm,b =0.57071 (3) nm,c=1.72977(9) nm,α=90°,β=94.3200(10)°,y=90°,R1=0.0296,wR2 =0.0801.在该配合物中,柔性二羧酸配体4-(3('-)羧丙酰胺基)苯甲酸阴离子桥联相邻的Cu(Ⅱ)离子形成一维链状结构,相邻链之间通过N-H…O和O-H…O氢键连接起来形成二维层状结构,层与层之间通过C-H…O氢键扩展成三维超分子结构.     

6，6‘—二甲氧基—4，5，4’,5‘—二亚甲基二氧基—2，2’—联苯二甲酸二甲酯及其衍生物的合成研究

以没食子酸为原料经酯化、醚化、区域选择性硝化、还原、Sanmeyer及分子间Ulmann耦合等反应以较高产率合成6,6‘-二甲氧基-4,5,4‘,5‘-二亚甲基二氧基-2,2‘-联苯二甲酸二甲酯（β-联苯双酸,β-DDB）,并对其进行衍生化,得到5个β-DDB的衍生物,用IR,^1H NMR和MS等鉴定了其结构,使用手性柱对β-DDB进行拆分得到了两个对映异体,利用圆二色谱确定了它们的立体构型。     

Direct optical resolution of the enantiomers of axially chiral compounds by high-performance liquid chromatography on cellulose tris-(3,5-dimethylphenylcarbamate) stationary phase

Summary The enantiomeric separation of nineteen biphenyl dimethyl dicarboxylate derivatives has been examined by HPLC on a chiral statonary phase prepared by coating aminopropylated silica gel with cellulose tris-(3,5-dimethylphenylcarbamate). It was found that trifluoroacetic acid (TFA) has a dominant effect on chiral separation for acidic compounds. The percentage of 2-propanol in the mobile phase does not have a large effect on the anantioselectivity but the separation was dramatically influenced by the kind of alcohol in the mobile phase. The effect of temperature on the chiral separation is also discussed. Most of the enantiomers investigated could be resolved satisfactorily.     

双三烃基锡1,1′-二茂铁二甲酸盐的合成及晶体结构

合成了１３个新的双三烃基锡１,１'－二茂铁二甲酸衍生物,并进行了化合物的波谱表征．Ｃｙ２ＭｅｓｎＯＯＣＦｃＣＯＯＳｎＭｅＣｙ２的Ｘ射线衍射单晶结构测定表明,其结构为单斜晶系,Ｆｄｄ２空间群,晶胞参数:α＝１．８７３ ５(４)ｎｍ,ｂ＝３．５９３ ０(７)ｎｍ,ｃ＝１．１１２ ２(２)ｎｍ;α＝β＝γ＝９０．００(０)°;Ｖ７．４８７(４)ｎｍ３;Ｚ＝８;Ｆ(０００)＝３ ５５２;最终可靠因子Ｒｔ＝０．０４８,Ｒｗ＝０．０５４．为五配位轻微畸变的三角双锥的线性聚合结构化合物．     

Syntheses,Structures, and Photoluminescence of Lanthanide Coordination Polymers Based on 4‐Oxo‐1,4‐dihydro‐2,6‐pyridinedicarboxylic acid

Investigating the coordination chemistry of H₂CDA (4‐oxo‐1,4‐dihydro‐2,6‐pyridinedicarboxylic acid) with rare earth salts Ln(NO₃)₃ under hydrothermal conditions, structure transformation phenomenon was observed. The ligand, H₂CDA charged to its position isomer, enol type structure, H₃CAM (4‐hydroxypyridine‐2,6‐dicarboxylic acid). Six new lanthanide(III) coordination polymers with the formulas [Ln(CAM)(H₂O)₃]_n [Ln = La ( 1 ), Pr, ( 2 )] and {[Ln(CAM)(H₂O)₃] · H₂O}_n [Ln = Nd, ( 3 ), Sm, ( 4 ), Eu, ( 5 ), Y, ( 6 )] were synthesized and characterized. The X‐ray structure analyses show two kinds of coordination structures. The complexes 1 and 2 and 3 – 6 are isostructural. Complexes 1 and 2 crystallize in the monoclinic C₂/c space group, whereas 3 – 6 crystallize in the monoclinic system with space group P2₁/n. In the two kinds of structures, H₃CAM displays two different coordination modes. The Sm^III and Eu^III complexes exhibit the corresponding characteristic luminescence in the visible region at an excitation of 376 nm.     

表层二氧化锆/硅基－CDMPC手性固定相的制备及联苯双酯类保肝药的直接拆分

用分子自组装的方法制备了表层纳米氧化锆包覆多孔微米硅球，得到的氧化锆 /硅胶微球用作高效液相色谱担体，本方法制备的担体具有氧化锆的表面特性并保 持了硅胶的颗粒均匀、表面积大、渗透性好的优点，可以制备大涂敷量的手性固定 相，以增加固定相的手性识别能力，以涂敷量为20%的纤维素－三（3，5-二甲基苯 基氨基甲酸酯）－氧化锆/硅胶手性固定相（CDMPC-coated ZrO_2/SiO_2）上，对 联苯双酯类保肝药物进行直接拆分，考察了流动相极性、第二种极性改性剂对样品 保留和拆分的影响；并对手性拆分机理进行了阐述，结果表明：CDMPC- ZrO_2/SiO_2手性固定相比CDMPC-ZrO_2具有更好的手性拆分能力。     

A Novel Coordination Polymer, [Ag4^1 （bpdc）（H2bpdc）（Hbpdc）2]n （bpdc = 2,2＇-bipyridyl-3,3＇-dicarboxylate）： Coordination Models of bpdc Ligands

A novel coordination polymer, [Ag₄ppdc)(H₂bpdc)(Hbpdc)₂] (bpdc = 2,2′‐bipyridyl‐3,3′‐dicarboxylate), was hydrothermally synthesized at 403 K and structurally characterized by single crystal X‐ray diffraction analysis. The compound crystalizes in the monoclinic space group C2/c with a=1.9516(4) nm, b=1.9503(4) nm. c=1.2566(3) nm, and β=112.48(3)°. In the two‐dimensional crystal structure, Ag^I center is coordinated, in a scarce coordination environment, double‐capped tetrahedron, by one bpdc ligand to form N‐Ag‐N chelate bond via two pyridyl N atoms, and other two bpdc ligands to form two O‐Ag‐O chelate bonds, respectively, via two carboxyl O atoms. The bpdc ligands are present in one non‐protonated form, bpdc, and two protonated forms, Hbpdc and H2bpdc, which all act as μ3‐ligand in a hexadentate fashion (N, N′; O, O′; O, O′) to coordinate with three Ag centers, respectively, through the three chelate bonds. This coordinated fashion of bpdc ligand is first found in the title compound. W‐Us‐NIR reflectance spectroscopy study revealed insulator nature for the crystal with an optical energy gap of 3.1 eV.     

Probing multiple melting behaviors in poly(ethylene naphthalene 2,6‐dicarboxylate) with different thermal histories by simultaneous wide‐angle and small‐angle X‐ray scattering

A simultaneous wide‐angle and small‐angle X‐ray scattering study of two poly(ethylene naphthalene 2,6‐dicarboxylate) samples crystallized from the glassy state at different annealing temperatures for different annealing times was carried out with synchrotron radiation. Either single or dual melting was induced in the samples, as confirmed by differential scanning calorimetry (DSC). The correlation function and interface distribution function were calculated to evaluate microstructural parameters such as the long spacing, the thickness of the amorphous and crystalline phases, and the width of the size distributions. The sample with dual melting behavior exhibited an abrupt increase of all microstructural parameters at temperatures above the melting of the lowest endotherm, whereas the sample revealing a single melting endotherm did not show such a sudden change. This finding agrees with the concept that the appearance of two melting peaks in DSC traces can be explained by the dual lamellar stacking model. © 2001 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 39: 881–894, 2001     

The Synthesis of α-DDB, β-DDB and Theoretical Study with AM1

Biphenyl units are present in a wide range of compounds both natural and synthetic, and many of them have pharmacological activity1. Xie Jingxi et al. found that dimethyl 4,4'-dimethoxy-5,6,5',6'-dimethylenedioxybiphenyl-2,2'-dicarboxylate((-DDB) as an important intermediate for the synthesis of Schizandrin C analogue which is effective in lowering elevated SGPT level2-3. Two isomers dimethyl 6,6'-dimethoxy-4,5,4',5'-dimethylenedioxybiphenyl-2,2'-dicarboxylate ((-DDB) and 6,4,-dimethoxy-4…     

A new linear bismuth coordination polymer based on 1,10‐phenanthroline‐2,9‐dicarboxylic acid: ionothermal synthesis,crystal structure and fluorescence properties

A new linear bismuth(III) coordination polymer, catena‐poly[[chloridobismuth(III)]‐μ₃‐1,10‐phenanthroline‐2,9‐dicarboxylato‐κ⁶O²:O²,N¹,N¹⁰,O⁹:O⁹], [Bi(C₁₄H₆N₂O₄)Cl]_n, has been obtained by an ionothermal method and characterized by elemental analysis, energy‐dispersive X‐ray spectroscopy, IR spectroscopy, thermal stability studies and single‐crystal X‐ray diffraction. The structure is constructed by Bi(C₁₄H₆N₂O₄)Cl fragments in which each Bi^III centre is seven‐coordinated by one Cl atom, four O atoms and two N atoms. The coordination geometry of the Bi^III cation is distorted pentagonal–bipyramidal (BiO₄N₂Cl), with one bridging carboxylate O atom and one Cl atom located in the axial positions. The Bi(C₁₄H₆N₂O₄)Cl fragments are further extended into a one‐dimensional linear polymeric structure via subsequent but different centres of symmetry (bridging carboxylate O atoms). Neighbouring linear chains are assembled via weak C—H...O and C—H...Cl hydrogen bonds, forming a three‐dimensional supramolecular architecture. Intermolecular π–π stacking interactions are observed, with centroid‐to‐centroid distances of 3.678 (4) Å, which further stabilize the structure. In addition, the solid‐state fluorescence properties of the title coordination polymer were investigated.