配位聚合物[Mn(4,4′-bpy)_(1.5)(H_2O)_3](ClO_4)·(4,4′-bpy)(L)·H_2O的水热合成和晶体结构(英文)

The title compound, [Mn(4,4'-bpy)1.5(H2O)3](ClO4)·(4,4'-bpy)(L)·H2O(1), where L=2,4,6-trimethylbenzoic acid, was synthesized and its crystal structure was determined by X-ray diffraction analysis. The crystal is of triclinic, space group P1 with a=2.929 9(6) nm, b=1.036 4(2) nm, c=8.222 0(1) nm, α=105.300(2)°, β=97.495(2)°, γ=91.118(2)°, V=1.884 0(4) nm3, Z=2, Mr=780.10, Dc=1.375 g·cm-3, μ=0.483 mm-1, F(000)=812, R=0.055 4, wR=0.135 2. The Mn atoms are octahedrally coordinated by three N atoms of three 4,4'-bipyridine ligands and three O atoms of water. The complex shows a one-dimensional chain structure bridged by water and 4,4'-bipyridine molecules. CCDC: 615707.     

Four Complexes of Mn(Ⅱ), Co(Ⅱ), Ni(Ⅱ) and Cu(Ⅱ) Based on 2-Morpholine-4-yl-4,6-di-pyrazol-1-yl-1,3,5-triazine

Three azide bridged complexes, namely, [Mn_2L_2(N_3)_4(H_2O)_2](1), [Co_2L_2(N_3)_4]·(H_2O)_3(2) and [Ni_2L_2(N_3)_3(H_2O)]N_3·(H_2O)_4(3)(L = 2-morpholine-4-yl-4,6-di-pyrazol-1-yl-1,3,5-triazine), were synthesized by the reaction of L ligand, sodium azide with Mn(Ⅱ), Co(Ⅱ) and Ni(Ⅱ) chlorides. The copper(Ⅱ) chloride combined with thiocyanate and L ligand to form a mononuclear complex [CuL(CH_3OH)(SCN)(NCS)](4). Complexes 1~4 were characterized by IR, elemental analysis and X-ray crystallographic analysis. It was worth noting that two Mn(Ⅱ) atoms were connected by the end-to-end mode in 1, while Co(Ⅱ) and Ni(Ⅱ) atoms were connected by the end-on mode in 2 and 3. In complex 4, the central copper atom was coordinated with a sulfur atom and a nitrogen atom of the two thiocyanate ligands, respectively. Hydrogen bonds, π-π stacking interactions, thermogravimetric analysis and fluorescence properties of 1~4 were studied.     

A Three-dimensional Tm(Ⅲ)-Zn(Ⅱ) Heteronuclear Metalorganic Framework Based on Imidazole-dicarboxylate Ligand:Synthesis,Crystal Structure and Luminescence Property

A d-f heteronuclear metal-organic framework(MOF),{[Tm_3Zn_6(bipy_2)_2(mimda)_7(H_2O)_3]·(H_2O)_5}_n(1,H3 mimda = 2-methyl-1-H-imidazole-4,5-dicarboxylic acid,and bipy = 4,4?-bipyridine),has been synthesized under solvothermal conditions,and structurally characterized by elemental analysis,IR spectra and X-ray single-crystal diffraction.It crystallizes in orthorhombic system,space group Pnma with a = 16.1102(9),b = 33.5805(19),c = 16.8593(10) ?,β = 97.344(11)°,V = 9120.7(9) ?~3,Z = 4,F(000) = 5184,the final R = 0.0530 and w R = 0.1306.In complex 1,the Tm(Ⅲ) ions adopt two types of coordination fashions.Complex 1 shows onedimensional(1-D) Tm-Zn heteronuclear zigzag chains,and these chains are further linked by H3 mimda ligands into Tm-Zn heteronuclear 2-D lattice-like arrays.The 2-D heteronuclear units were connected through [Zn_6(mimda)_6] rings to give rise to the Tm-Zn heteronuclear cages.Finally,H3 mimda ligands connected the cages into a 3-D heterometallic framework by the combination of [TmO_7]_n and Tm-Zn heteronuclear cages.In addition,the thermal stability and luminescent property have been investigated.     

有机二磺酸锰配合物(英)

The crystal structure of [Mn(BDA)(bpy)₂(H₂O)](H₂O)₂ (1)(BDA=6,6′-dibromo-2,2′-dimethoxy-1,1′-binaphthylene-4,4′-disulfonate, bpy=2,2′-bipyridine) composes of a manganese center which is surrounded by two nitrogen atoms from 2,2′-bipyridine and four oxygen atoms from three water and sulfonate group of BDA that also participate in H-bonding interactions to form 3D network as well as some uncoordinated water. CCDC: 277922.     

Synthesis and Fluorescent and Magnetic Properties of a New Europium Complex Eu(C_(20)H_(14)O_3N)_3(2,2'-bipy)(H_2O)·H_2O

A new europium(Ⅲ) complex Eu(C_(20)H_(14)O_3N)_3(2,2?-bipy)(H_2O)·H_2O has been synthesized with2-diphenylanine carbonyl benzoic acid and 2,2?-bipyridine as ligands.Crystal data for the complex are as follows:triclinic,space group ■,a=11.3334(5),b=16.0883(7),c=17.0116(8)?,α=70.411(4)o,β=82.435(4)o,γ=85.095(4)o,V=2894.0(2)?~3,D_c=1.484 g/cm~3,Z=2,μ=1.15 mm~(-1),F(000)=1320 and the final R=0.0447 and w R=0.0578.The Eu(Ⅲ) ion is coordinated by nine atoms to give a monocapped square antiprism coordination geometry.The complex shows two intense fluorescence emission bands arising from the transitions of Eu~(3+):~5D_0→~7F_1 (592 nm) and ~5D_0→~7F_2 (616 nm),respectively.Also reported is the magnetic property of the complex.The complex exhibits antiferromagnetism in the temperature range of 300～2 K.     

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

A new nickel(Ⅱ) complex Ni_2(L)_2(2,2?-bipy)2·5.5H_2 O 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) ?, α = 70.715(5), β = 80.599(5), γ = 77.383(6)o, V = 1989.4(8) ?3, Dc = 1.531 g/cm3, 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 N_2O_3, giving a distorted square pyramidal geometry. The thermal stability and electrochemical properties of the complex were investigated.     

Syntheses, Characterization and Crystal Structures of Two-dimensional 4,4＇-Bipyridyl Lead Halides, PbI2 （4,4＇-bpy） and PbBr2 （4,4＇-bpy）

Two-dimensional 4,4-bipyridyllead halides, Pbl2 (4,4‘-bpy) (1) and PbBr2 ( 4,4‘-bpy ) (2), were synthesized. The structures were determined by means of X-ray single crystal diffraction. The structure shows a distorted octahedral configuration with six-coordinated central lead atoms. In crystals 1 and 2, the molecules are packed in a two-dimensional network structure through bridging halide atoms and 4,4‘-bipyridine ligands between the adjacent lead atoms.     

A 3D Nickel(Ⅱ) Complex Constructed by Bis(2-dimethylaminoethyl) Ether: Solvothermal Synthesis,Crystal Structure and Catalytic Properties

Treatment of bis(2-dimethylaminoethyl) ether(BDMAE) with nickel acetate afforded a novel 3D nickel(Ⅱ) complex [Ni(BDMAE)(H_2O)_3·(CH_3COO)_2·(H_2O)_2] under solvothermal conditions. Its crystal structure was characterized by elemental analysis, IR spectrum, PXRD and single-crystal X-ray diffraction analysis. The complex belongs to the orthorhombic system, space group C2221 with a=8.823(2), b=13.932(3), c=17.563(4) ?, V=2158.9(8) ?~3, Z=4, C_(12)H_(36)N_2NiO_(10), Mr=427.14, Dc=1.314 g/cm~3, F(000)=920 and μ=0.944 mm~(-1). Single-crystal X-ray diffraction reveals that the mononuclear nickel(Ⅱ) ion is six-coordinated to one oxygen, two nitrogen atoms of the BDMAE ligand and three oxygen atoms of coordinated water molecules. The complex exhibits a 3D supramolecular structure through a variety of intermolecular and intramolecular hydrogen bonding interactions. In addition, the complex has been investigated for catalytic properties towards the Henry reaction of nitromethane with p-nitrobenzaldehyde, and the results indicated that the 1-p-nitrophenyl-2-nitroethanol product was obtained in excellent yield under optimum conditions with the complex as the catalyst.     

Synthesis and Crystal Structure of a 1-D Chain Coordination Complex {[Mn2(HCAM)3(H2bipy)]·5H2O}n

The 1-D chain coordination complex of {[Mn2(HCAM)3(H2bipy)]·5H2O}n(H3CAM=4-hydroxypyridine-2,6-dicarboxylic acid,bipy=4,4′-bipyridine) has been synthesized by the reaction of 4-hydroxypyridine-2,6-dicarboxylic acid,4,4′-bipyridine and manganese carbonate under hydrothermal conditions,and its crystal structure was determined by X-ray diffraction method.The crystal belongs to the monoclinic system,space group P21/n with a=10.110(2),b=20.159(4),c=17.861(4) ,β=99.67(3)°,V=3.5884(12) nm3,Mr=901.47,Z=4,Dc=1.669 g·cm-3,μ=0.798 mm-1,F(000)=1840,the final R=0.0713 and wR=0.1853.The complex forms a 1-D chain bridged by HCAM,protonated 4,4-bipyridines link the 1-D chains to construct 2-D networks via N-H…O hydrogen bonds,and networks are further extended via π-π stacking and hydrogen bonds into 3-D supramolecular framework.     

Syntheses,Structures and Properties of Three Novel La(Ⅲ)/Co(Ⅱ) Coordination Polymers Based on 5-(3-(Tetrazo-5-yl)phenyl)isophthalic Acid

Three novel complexes, namely {[La(tapipa)(4,4′-bibp)·(H_2O)_2]·H_2O}n(1), {[La-(tapipa)(H_2O)_4(OH)]·3 H_2O}n(2), [Co(tapipa)(1,4-bbib)]n(3)(tapipa = 5-(3-(tetrazo-5-yl)phenyl)isophthalic acid, 4,4′-bibp = 4,4′-bis(imidazolyl)biphenyl, and 1,4-bbib = 1,4-bis(benzimidazo-1-ly)benzene) have been synthesized under solvothermal conditions and characterized by PXRD, IR,TGA, and so on. Complex 1 presents a 2 D layer structure, which is finally packed into a 3 D supramolecular structure by means of hydrogen bonds; complexes 2 and 3 exhibit 1 D chains and 2 D wavy-type structures, respectively, which are expanded into 3 D supramolecular structures through hydrogen bonds and π-π interactions. Furthermore, the luminescence properties of complex 1 and the variable-temperature magnetic susceptibilities of 3 were investigated. Complex 1 has highly selective sensing for Fe~(3+) and Cr_2O_7~(2-) ions.     

Two Zn~Ⅱ Coordination Polymers with 2,2?-Oxybis(benzoic acid) and Different N,N?-Donor ligands

Two new Zn~Ⅱ coordination polymers [Zn(oba)(4,4?-bipy)]n(1) and [Zn(oba)-(bpe)_(1/2)(H_2O)]_n(2)(H_2oba = 2,2?-oxybis(benzoic acid), 4,4?-bipy = 4,4?-bipyridine, bpe = 1,2-bis(4-pyridyl)ethylene) were synthesized by hydrothermal reactions and characterized by single-crystal X-ray diffraction, thermogravimetric analysis, IR spectroscopy and elemental analysis. Complex 1 shows a 3D metal-organic framework with a uninodal 4-connected 65.8 dmp network. Complex 2 features 1D ladder-shaped chains, which are further connected into a 2D stair-step network through intermolecular O–H···O hydrogen bonds.     

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.     

Synthesis and Crystal Structure of a Novel Ca(Ⅱ) Coordination Polymer Containing Dipyridine Dicarboxylic Ligand

The novel alkaline metal complex Ca(BPDCH)2(1, BPDCH2 = 2,2'-bipyridine-5,5'-dicarboxylic acid) has been synthesized by the hydrothermal reaction of Ca(NO3)2·4H2O with 2,2'-bipyridine-5,5'-dicarboxylic acid. The molecular and crystal structures of complex 1 have firstly been characterized by FTIR, elemental analysis, and X-ray single-crystal diffraction. The 3D MOF structure of complex 1 was interpreted by the versatile binding modes-the intermolecular hydrogen bonds and π-π stacking interactions of 2,2'-bipyridine-5,5'-dicarboxylic acid ligand. The analysis results show complex 1 belongs to a coordination polymer with 3D MOF structure. The results of thermogravimetric analysis and solubility demonstrate complex 1 is a thermostable compound and does not dissolve in water and traditional organic solvents.     

Mixed-ligands Self-assembly Strategy Affording a New 4-Fold Interpenetrated 3D Co(Ⅱ)-based Coordination Polymer: Synthesis,Crystal Structure and Magnetic Property

A new Co(Ⅱ)-based coordination polymer, namely [Co(L)_(0.5)(4,4?-bipy)_(0.5)(H_2 O)_2]_n(1,H_4 L = 1,3-di(3?,5?-dicarboxylphenyl)benzene, 4,4?-bipy = 4,4?-bipyridine), has been hydrothermally synthesized using the mixed-ligands self-assembly strategy and further fully characterized. The crystal structure is of monoclinic, space group C2/c with a = 18.9124(10), b = 11.6150(5), c =15.4380(6) ?, β = 110.989(5)°, V = 3166.2(2) ?~3, C_(16) H_(13) CoNO_6, M_r = 374.20, Z = 8, D_c = 1.570 g·cm–3, F(000) = 1496, μ = 1.116 mm~(–1), R = 0.0461 and wR = 0.1312 for 2328 observed reflections(I 2s(I)). The crystal structure analysis revealed that 1 is a 4-fold interpenetrated three-dimensional(3D) framework with(3,4)-connected dmd-type topology. Moreover, the thermal stability and magnetic property of 1 were also investigated.     

SYNTHESIS AND CRYSTAL STRUCTURE OF [(η~5-C_5H_5)_2NdCl·OC_4H_8]_2

All attempts to prepare light lanthanide dicyclopeutadienyt chloride failed,due to the disproportionation reaction. The crystal complex of [(η~5-C_5H_5)_2NdCl.OC_4H_8]_2 was successfully prepared by the reaction of NdCl_3·2C_4H_8O with cyclopentadienyl sodium (molar ratio 1:1.8)in tetrahydrofuran at room temperatureThe composition of the title compound was determined by the methods of elemental analysis, infrared spectroscopy and photoelectron spectroscopy. The crystal structure of [(η~5-C_5H_5)_2NdCl·OC_4H_8]_2 was determined from single crystal X-ray diffraction. Data were collected at-60℃ under dry nitrogen atmosphere.The complex crystallizes in the monoclinic space group P2_1/c,with Z=2. Lattice parameters are: a=8.201(3), b=21.589(6),c=8.596(3),β=109.10(3)°.The structure was solved by Patterson and Fourier techniques and refined by least-squares to a final conventional R=0.0636 for 1680 reflections. There are two Nd atoms in the dimeric unit which are bridged asymmetrically by the two chlori     

Two Cu(Ⅱ) Complexes with Hydrolyzed Nicotinamide Ligand: Crystal Structures and Bioactivities

Two Cu(Ⅱ) complexes of [Cu(2,6-DPC)(Hnta)(H_2O)]·H_2O(2,6-DPC = 2,6-pyridinedicarboxylic-carboxylate, Hnta = nicotinic acid) and [Cu_2(2,4-D)_4(Hnta)_2](2,4-D = 2,4-dichlorophenoxyacetic-carboxylate) were synthesized and successfully obtained as single crystals in this paper. The supramolecular structures of the complexes from zero to three dimensions and the weak intermolecular force in the crystal were analyzed. The single-crystal structures of the complexes were further analyzed by Hirshfeld surface analysis. The competition capacity of the complexes about calf thymus DNA(ct-DNA) was also analyzed by fluorescence spectroscopy. The ability of complexes to cleave the plasmid DNA(pBR322-DNA) was determined by gel electrophoresis assay. And at last, the complexes' cytotoxic activities were reviewed for four kinds of cancer cell lines(HeLa, MCF-7, HepG, SKOV-3), showing that the coordination polymer has anti-tumor activity and cytotoxicity.     

Synthesis,Crystal Structure,Fluorescent Property and DFT Study of a Novel 1D Polymer [Zn(HMICD)(bpy)]_n·2nH_2O

A new one-dimensional(1D) polymer, [Zn(HMIDC)(bpy)]_n·2n H_2O(1, H_3MIDC = 2-methyl-imidazole-4,5-dicarboxylic acid, bpy = 2,2?-bipyridine), has been solvothermally synthesized and characterized by single-crystal X-ray diffraction, elemental analysis, IR spectroscopy, UV-vis spectrum and fluorescence measurements. Complex 1 crystallizes in orthorhombic system, space group Pbca with a = 14.404(3), b = 8.6900(17), c = 26.570(5) ?, V = 3325.8(11) ?~3, Dc = 1.700 g/cm~3, M_r = 425.70, Z = 8, F(000) = 1744, μ = 1.522 mm~(-1), the final R = 0.0421 and w R = 0.1018. The Zn(Ⅱ) ion is six-coordinated by O and N atoms from one HMIDC ligand, two O atoms from another HMIDC ligand and two N atoms from the bpy ligand. The HMIDC anion, which acts as a tetradentate ligand, chelates two Zn ions to form a one-dimensional(1D) zigzag chain structure. We analyzed the electronic structure and orbital energies of complex 1 by DFT methods, and the results are consistent with the UV-vis spectrum. And we also discussed the luminescent mechanism of complex 1 in detail.     

A New 3-D Sr(Ⅱ) Complex:Two-step Solvothermal Synthesis,Structure and Luminescent Properties

The title complex [HSr_3(pda)_3(H_2O)_3Cl]n(1, H_2pda = pyridine-2,6-dicarboxylic acid) has been prepared under two-step solvothermal conditions. It has been characterized by X-ray single-crystal diffraction, IR, TGA-DSC and elemental analysis. The crystal belongs to the trigonal system, space group R-3 with a = 14.484(2), b = 14.484(2), c = 21.970(4) ?, γ = 120 o, V = 3991.4(11) ?~3, C_(21)H_(16)ClN_3O(1)_5Sr_3, M_r = 848.68, Z = 6, Dc = 2.118 g/cm~3, μ = 6.175 mm~(-1), F(000) = 2484, the final R = 0.0457 and w R = 0.1139. This complex possesses a 3-D structure constructed from [HSr_3(pda)_3(H_2O)_3Cl]_2 units and connected by coordinated carboxylate groups of pda2-ligands. The topology symbol of this network is(4~(12)6~3). Luminescent property of the title complex has been investigated at room temperature.     

Synthesis,Structure and Characterization of a New Complex: [Mn(C_6H_(12)N_4)_2(H_2O)_4][Mn(H_2O)_6][SO_4]_2·6H_2O

A novel complex,[Mn(C_6H_(12)N_4)_2(H_2O)_4][Mn(H_2O)_6][SO_4]_2·6H_2O,was synthesized and hexagonal single crystals with centimeter-scale sizes were obtained by the method of solvent evaporation.It was characterized by elemental analysis,infrared spectrum,thermogravimetric analysis and X-ray single-crystal diffraction.The complex belongs to triclinic crystal system,space group P■ with a=9.3390(8),b=13.3520(13),c=16.3207(13)?,α=100.7160(3)°,β=90.1020(10)°,γ=109.9490(5)°,V=1874.9(3)?~3,Z=2,D_c=1.542 g/cm~3,M_r=870.64,μ=0.876 mm~(-1),T=293(2) K,F(000)=916 and S=0.990.The crystal structure determination displayed a distorted octahedral geometry around the manganese atom,which is bound to two nitrogen atoms from hexamethylenetetramine,acting as monodentate ligands,and to four aqua ligands.Variable-temperature magnetic measurements of the complex indicate the presence of weak antiferromagnetic interaction between manganese centers.     

Structures and Properties of Two Pillared-layer Mn(Ⅱ) MOFs with 5-Ethyl-pyridine-2,3-dicarboxylate

The reaction of Mn(OAc)2·4 H2 O, 5-ethyl-pyridine-2,3-dicarboxylic acid(H2 epda) and 4,4?-bipyridine(4,4?-bipy)/4,4?-bis(imidazolyl)biphenyl)(bibp) under hydrothermal conditions produced two new manganese(Ⅱ) MOFs [Mn(epda)(4,4?-bipy)1/2](1) and [Mn(epda)(bibp)1/2](2), which were characterized by elemental analysis, infrared spectroscopy, thermogravimetric analyses, and single-crystal X-ray diffraction. The structures of complexes 1 and 2 are similar. In 1, the adjacent Mn(Ⅱ) ions are connected by epda dianion to generate a 2 D(4,4) grid layer, and such 2 D layers are further connected via bibp ligand to form another layer, forming a 2 D pillared-layer. Topologically, the Mn atoms as the node are bridged by the edpa anions and bibp ligands to form a uninodal 5-connected network topology. The magnetic properties of 1 and 2 have also been-investigated, and the exchange interctions were –1.39 and –1.05 cm1, respectively. According to the crystal structures, compounds 1 and 2 were carried out by using hybrid DFT methods at the B3 LYP/6-31 G(d) level. The DFT-BS approach was applied to study the magnetic coupling behaviors for 1 and 2. The result reveals that the calculated exchange coupling constants J were in good agreement with the experimental data.