Synthesis and Crystal Structure of Trans-bis(acesulfamato-O)tetraaquazinc(Ⅱ)

<正>The title compound,trans-bis(acesulfamato-O)tetraaquazinc(Ⅱ)(I,C_8H_(16)N_2O_(12)S_2Zn), crystallizes in the triclinic system,space group P_1~-with a=5.1638(5),b=8.5338(9),c=9.9583(9) (?),a=74.325(8),β=81.112(7),γ=75.800(8)°,V=407.77(7)(?)~3,Z=1,F(000)=236,R_(int)=0.085, T=296 K,the final R=0.029 and wR=0.078 for 1832 observed reflections with I2σ(I).The Zn~Ⅱcentre resides on a centre of symmetry and has a distorted octahedral geometry.The basal plane is defined by two carbonyl O atoms of two monodentate trans-oriented acesulfamato ligands and two trans-aqua ligands.The axial positions in the octahedron are occupied by two trans-aqua ligands. Intermolecular O-H…O hydrogen bonds produce R_2~2(8)and R_2~2(16)rings,which lead to two-dimensional polymeric chains.     

A concise modular synthesis of 2,5-diethynyl-3,4-dibutyl-thiophene-bridged back-to-back terpyridine ligands

The efficient synthesis of soluble and rigid terpyridine-based ditopic ligands bearing an increasing number of 2,5-diethynyl-3,4-dibutylthiophene (DEDBT) modules has demonstrated the advantages of a single convergent strategy based on a double coupling in a final step of monoterpyridine building blocks carrying the adequate number of thiophene modules with a diiodo-substituted thiophene subunit. This protocol enjoys the advantages of both efficiency and versatility and requires pivotal intermediates, which were produced by a step-by-step implementation of monoterpyridine fragments with a key thiophene intermediate carrying an iodo function, a propargylic-protecting group, and two butyl-solubilizing fragments. One set of experimental conditions is required to produce all the intermediates and the final ligands. Oxidative dimerization of monosubstituted terpyridine skeletons bearing one or two thiophene substituents and a terminal alkyne function, in the presence of cupric salts and oxygen, afforded the homotopic ligands with a central dithienylbutadiyne spacer. Optical properties for the new oligomers have been investigated and are discussed in terms of effective conjugation length and pi-electron conjugation. Upon increasing the number of interspersed DEDBT units, a significant lowering in energy of absorption and fluorescence transitions as well as of the quantum yields is observed.     

对甲酰基苯氧乙酸和2-氨基苯并噻唑的新型三元铜配合物的合成、晶体结构及抗微生物活性

以对甲酰基苯氧乙酸和2-氨基苯并噻唑为原料,合成了一种三元铜配合物,并通过元素分析, 红外光谱以及X-射线衍射单晶结构分析对其进行了表征。该配合物晶体属单斜晶系,P2₁/c空间群,中心铜(Ⅱ)离子的配位数为4,分别与2个对甲酰基苯氧乙酸配体分子的羧基和2个2-氨基苯并噻唑配体分子的噻唑环上的氮原子发生配位。抑菌实验结果表明,配合物对新型隐球菌、粘性红圆酵母、桔青霉和黑曲霉具有很好的抑制作用,而对大肠杆菌和金黄色葡萄球菌的抑制效果一般。     

bis(nicotinamide) and bis(N,N-diethyl nicotinamide) p-hydroxybenzoate complexes of Ni(II), Cu(II) AND Zn(II)

The mixed-ligand p-hydroxybenzoate complexes of Ni(II), Cu(II) and Zn(II) with nicotinamide and N,N-diethylnicotinamide were synthesized and characterized by elemental analysis, magnetic susceptibility measurements and mass spectrometry. The thermal behavior of the complexes was studied by simultaneous TG, DTG and DTA methods in static air atmosphere. The infrared spectral characteristics of the complexes are also discussed. The complexes contain two water molecules, two p-hydroxybenzoato (p-hba) and two nicotinamide (na) (or diethylnicotinamide (dena)) ligands per formula unit. In these complexes, all ligands are coordinated to the metal ion as monodendate ligands. In Zn(II)-na and Cu(II)-dena complexes, thep-hydroxybenzoate behaves as bidentate chelating ligand through carboxylic oxygen atoms. The decomposition pathways and the stability of the complexes are interpreted in the terms of the structural data. The final decomposition products were found to be the respective metal oxides. This revised version was published online in July 2006 with corrections to the Cover Date.     

Synthesis,Crystal Structure and Antimicrobial Activity of a New Ternary Copper(Ⅱ) Complex with p-Chlorophenoxyacetic Acid and 2-Amino Benzothiazole

A novel ternary complex of Cu(pcpa)2(aben)2 (pcpa=p-chlorophenoxyacetic acid anion,aben=2-amino benzothiazole) was synthesized by the reaction of copper acetate,2-amino benzothiazole and p-chlorophenoxyacetic acid.Elemental analysis,IR,UV and X-ray single-crystal diffraction were carried out to determine the composition and crystal structure.The crystal crystalli-zes in the monoclinic system,space group C2/c with a=25.795(4),b=7.384(3),c =17.741(6),β=107.47(2)°,C30H24Cl2CuN4O6S2,Mr=735.09,V=3223.2(18) 3,Z=4,Dc=1.515 Mg/m3,λ(MoKα)=0.71073 ,μ=1.022 mm-1,F(000)=1500,the final R=0.0464 and wR=0.1244.A total of 3218 unique reflections were collected,of which 2228 with I 2σ(I) were observed.The Cu(II) atom is four-coordinated with two carboxylate oxygen atoms of the two pcpa ligands and two nitrogen atoms in thiazole rings of two aben ligands.The analysis of crystal structure shows intermolecular and intramolecular hydrogen bonds between amino-nitrogen atoms of the two aben ligands and carboxylate oxygen atoms of the two pcpa ligands.The antimicrobial properties of the title complex and its two free ligands were tested against representative bacterial and fungal strains.Results show that the antibacterial activity of the complex is less than or equal to that of 2-amino benzothiazole,but for yeasts and moulds,it exhibits excellent inhibitory effect better than that of its two free ligands.     

Synthesis and Crystal Structure of a Novel 1D Magnesium(II) Coordination Polymer Constructed by L-Cysteic Acid

A novel coordination polymer [Mg(L)(H2O)2]·H2O] (LH2 = L-cysteic acid) has been synthesized and characterized by elemental analysis, IR and single-crystal X-ray diffraction. The crystal crystallizes in orthorhombic system, space group P212121, with a = 5.962(3), b = 11.224(6), c = 13.664(7) , V = 914.3(8) 3, Z = 4, Mr = 245.50, Dc = 1.783 g/cm3, μ = 0.445 mm–1, flack parameter = 0.32(16), F(000) = 512, the final R = 0.0458 and wR = 0.1172 for 1578 observed reflections with I > 2σ(I). The Mg(II) atom shows an octahedral geometry defined by two carboxyl O atoms from two different L-cysteic acid ligands, one carboxyl O atom and one amino N atom from the adjacent ligand, and two aqua ligands. The Mg(II) atoms are bridged by L-cysteic acid ligands, leading to a 1D infinite zigzag chain. In the structure there are extensive hydrogen bonds, through which the complex completes its 3D framework structure.     

Ligand-mediated formation of Cu/metal oxide hybrid nanocrystals with tunable number of interfaces

Combining domains of different chemical nature within the same hybrid material through the formation of heterojunctions provides the opportunity to exploit the properties of each individual component within the same nano-object; furthermore, new synergistic properties will often arise as a result of unique interface interactions. However, synthetic strategies enabling precise control over the final architecture of multicomponent objects still remain scarce for certain classes of materials. Herein, we report on the formation of Cu/MO_x (M = Ce, Zn and Zr) hybrid nanocrystals with a tunable number of interfaces between the two domains. We demonstrate that the organic ligands employed during the synthesis play a key role in regulating the final configuration. Finally, we show that the synthesized nanocrystals serve as materials platforms to investigate the impact of the Cu/metal oxide interfaces in applications by focusing on the electrochemical CO₂ reduction reaction as one representative example.

We report on the formation of Cu/metal oxide hybrid nanocrystals with a tunable number of interfaces between the two domains. We demonstrate that the organic ligands employed during the synthesis play a key role in regulating the final configuration.     

Synthesis and Crystal Structure of a Novel 1D Magnesium (Ⅱ) Coordination Polymer Constructed by L-Cysteic Acid

A novel coordination polymer [Mg(L)(H2O)2]·H2O] (LH2=L-cysteic acid) has been synthesized and characterized by elemental analysis, IR and single-crystal X-ray diffraction.The crystal crystallizes in orthorhombic system, space group P212121, with a=5.962(3), b=11.224(6), c=13.664(7)(A), V=914.3(8) (A)3, Z=4, Mr=245.50, Dc=1.783 g/cm3,μ=0.445 mm-1,flack parameter=0.32(16), F(000)=512, the final R=0.0458 and wR=0.1172 for 1578 observed reflections with I ＞ 2σ(Ⅰ). The Mg(Ⅱ) atom shows an octahedral geometry defined by two carboxyl O atoms from two different L-cysteic acid ligands, one carboxyl O atom and one amino N atom from the adjacent ligand, and two aqua ligands. The Mg(Ⅱ) atoms are bridged by L-cysteic acid ligands, leading to a 1D infinite zigzag chain. In the structure there are extensive hydrogen bonds,through which the complex completes its 3D framework structure.     

Enantioselective alkynylation of aldehydes catalyzed by [2.2]paracyclophane-based ligands

[reaction: see text] [2.2]Paracyclophane-based ketimine ligands were evaluated as catalysts for the enantioselective addition of in situ-prepared alkynylzinc reagents to aldehydes. The initial high activity and enantioselectivity of these ligands could be improved by an additive screening. The final protocol gives chiral propargyl alcohols in up to >98% ee.     

Association of two 3D QSAR analyses. application to the study of partial agonist serotonin-3 ligands.

CATALYST and COMFA, two software packages for 3D QSAR studies, were associated to correlate the three-dimensional structures of 75 serotonin 5-HT3 ligands to their biological affinities. The conformational analysis and the influence of chemical function-based alignments (the basis of this association) on final results are discussed in this publication. These two analyses allow for precisely quantitating the weights of significant chemical groups or functions on the biological affinities.     

Synthesis,Crystal Structure and Characterization of a New Coordination Polymer from the Self-assembly of CoCl_2 Salt and Flexible Ligand 1,3-Bis（4-pyridyl）propane

A new 1D coordination polymer [Co(bpp)3Cl2(H2O)2]n 1 (bpp = 1,3-bis(4-pyridyl)-propane) was synthesized and characterized by elemental analysis,IR spectrum and single-crystal X-ray diffraction. The crystal belongs to the orthorhombic system,space group Ibca with a = 16.569(9),b = 17.240(10),c = 27.087(16) ,V = 7738(8) 3,Z = 8,Dc = 1.306 g/cm3,Mr = 760.65,λ(MoKa) = 0.71073 ,μ = 0.623 mm1,F(000) = 3192,the final R = 0.0678 and wR = 0.2011. The Co(II) atom is coordinated in a slightly distorted octahedral CoN4Cl2 geometry by two Cl atoms in the axial positions,four N atoms from the two bridging bpp ligands and two pendant bpp ligands. The CoN4Cl2 octahedra are connected by the bridging bpp ligands to form a 1D neutral coordination polymer chain. The chains are linked by face-to-face π-π interactions between adjacent pendant bpp ligands to give rise to a 3D supramolecular architecture. The photoluminescent investigation indicates that the emission of 1 is attributed to ligand-centered emission. The variable-temperature magnetic susceptibility measurement shows weak antiferromagnetic behavior in the complex.     

Mixed ligand complexes of coumarilic acid/nicotinamide with transition metal complexes

Coumarilate–nicotinamide complexes of Co^II and Zn^II were synthesized and investigated by elemental analysis, magnetic susceptibility, solid state UV–Vis, direct injection probe mass spectra, FTIR spectra, thermoanalytic TG-DTG/DTA, and crystal X-ray diffraction methods. It was obtained that both complex structures contain 2 mol aqua ligands, 2 mol coumarilate (CCA^?) and 2 mol nicotinamide (NA) ligands per formula unit. The CCA^? and NA ligands were bonded to metal cations as monodentate through acidic oxygen and nitrogen of pyridine ring, respectively. Thermal decomposition of each complex starts with dehydration and continue removing of 1 mol NA ligand. The thermal dehydration of the complexes takes place in one or two steps. The decomposition mechanism and thermal stability of the investigated complexes are interpreted in terms of their structures. The final decomposition products are found to be metal oxides.     

Synthesis, crystal structure and antiradical effect of copper(II) Schiff base complexes containing five-, six- and unusual seven-membered rings

The synthesis and solid-state structure of mononuclear copper(II) complexes [Cu(SAIB)(H(2)O)(2)] (1), [Cu(SBAIB)(H(2)O)(2)]·H(2)O (2) and [Cu(SGABA)(H(2)O)(2)] (3) are described. Schiff base ligands H(2)SAIB, H(2)SBAIB and H(2)SGABA chelate the copper(II) ion in an O,N,O tridentate fashion. The square-pyramidal geometry of the final complexes is completed by two water ligands. The formation of an unusual seven-membered ring in the set of copper(II) N-salicylidene-aminoacidates is reported. Compounds 1-3 were evaluated by the antiradical activity assay.     

Synthesis of binuclear platinum complexes containing the ligands 8-naphthyridine, 2-aminopyridine, and 7-azaindolate. An experimental study of the steric hindrance of the bulky pentafluorophenyl ligands in the synthesis of binuclear complexes

The bidentate N-donor ligands 2-aminopyridine (2-ampy), 7-azaindolate (aza) and 1,8-naphthyridine (napy) have been used to study the steric effect of pentafluorophenyl groups in the synthesis of binuclear platinum(II) complexes. The 2-ampy and aza ligands bridge two "Pt(C 6F 5) 2" fragments with Pt...Pt distances of 4.1 and 3.4 A, respectively (complexes 1 and 3). Under the same reaction conditions the napy ligand shows chelating behavior and makes the mononuclear complex ( A) highly reactive because of its strained coordination. One of the Pt-N bonds of the chelating complex is broken on reaction with HX {X = Cl ( 4), Br ( 5)} because of protonation while the anion X (-) occupies a created vacant site. The resulting mononuclear complex eliminates C 6F 5H when refluxed, and a binuclear complex ( 6) with two napy ligands bridging two "Pt(C 6F 5)Cl" fragments is obtained. The reaction of A with HPPh 2 affords a mononuclear complex ( 7) analogous to complexes 5 and 6, but reflux gives a binuclear complex ( 8) with the two napy ligands terminally bound and the PPh 2 groups bridging the "Pt(C 6F 5)napy" moieties. The reaction of A with HCCPh gives a binuclear complex; moreover, the final product does not depend on the ratio of complex A to HCCPh. Complexes 1, 4, 6, 9 have been structurally characterized by X-ray diffraction.     

Synthesis and Crystal Structure of a Novel Two-dimensional Layered Polymer [Zn（μ-O2CCH=CHCO2）（C3H4N2）（H2O）]n

1 INTRODUCTION More than 200 known metalloenzymes of a wide variety of types have been shown to contain zinc centers at their active sites (such as hydrolases, ligases and anhydrases)[1～3]. The active zinc centers in biological systems are usually surro…     

Synthesis and Characterization of a 1-D Zigzag Catenarian Compound [Sn（edt）2（p-phenylenediamine）]n

1 INTRODUCTION In recent years, the researches on tin sulfide ma- terials have drawn increasing attention of chemists owning to their potential applications as photo-vol- taic materials, holographic recording system[1, 2], so- lar control devices[3] and semiconductor materials. In the last decades, many finite adducts of tin (IV) thio- lates with organic amine ligands have been synthe- sized by self-assembly, such as cis-Sn(SPh)4(2,2?-bi- py)[4], cis-Sn(edt)2(ethyldimiane)[5], trans-Sn(…     

The role of the Auger parameter in XPS studies of nickel metal, halides and oxides

The critical role of the Auger parameter in providing insight into both initial state and final state factors affecting measured XPS binding energies is illustrated by analysis of Ni 2p(3/2) and L(3)M(45)M(45) peaks as well as the Auger parameters of nickel alloys, halides, oxide, hydroxide and oxy-hydroxide. Analyses of the metal and alloys are consistent with other works, showing that final state relaxation shifts, ΔR, are determined predominantly by changes in the d electron population and are insensitive to inter-atomic charge transfer. The nickel halide Auger parameters are dominated by initial state effects, Δε, with increasing positive charge on the core nickel ion induced by increasing electronegativity of the ligands. This effect is much greater than the final state shifts; however, the degree of covalency is reflected in the Wagner plot where the more polarizable iodide and bromide have greater ΔR. The initial state shift for NiO is much smaller than those of Ni(OH)(2) or NiOOH and the effective oxidation state is much less than that inferred from the average electronegativity of the ligand(s). Auger parameter analysis indicates that the bonding in NiO appears to have stronger contributions from initial state charge transfer from the oxygen ligands than that in the hydroxide and oxyhydroxide consistent with the considerable differences in the Ni-O bond lengths in these compounds with some relaxation of this state occurring during final state phenomena. The Auger parameter of NiOOH is, however, shifted positively, like the iodide, indicating greater polarizability of the ligands and covalency in this bonding. There is support for more direct use of relative bond lengths in interpreting differences between related compounds rather than more general electronegativity or similar parameters.     

Solution- and solid-phase syntheses of guanidine-bridged, water-soluble linkers for multivalent ligand design

[reaction: see text] Efficient syntheses of guanidine-bridged poly(ethylene glycol) linkers of various lengths in fully protected form are reported for both solution- and solid-phase protocols. The application of such linkers in the construction of water-soluble and high-affinity multivalent ligands against cholera toxin is demonstrated. Synthetic intermediates for multivalent ligands as large as 20 kDa in molecular weight have been assembled using presynthesized linkers. The final ligands are highly water-soluble, thus enabling proper biophysical characterization.     

Synthesis and Crystal Structure of a Novel Two-dimensional Layered Polymer

The title complex [Zn(μ-O2CCH=CHCO2)(C3H4N2)(H2O)]n was prepared by the reaction of zinc carbonate with maleic acid and imidazole in an aqueous-alcohol solution at 333 K, and its crystal structure has been solved by single-crystal X-ray diffraction. The complex crystallizes in the monoclinic system, space group Pc with a = 5.3858(7), b = 22.685(3), c =7.6782(1) A, β = 92.261(2)°, V = 937.4(2) A3, Z = 1, C14H16N4O10Zn2, Mr= 531.05, Dc= 1.882g/cm3,μ = 2.623 mm-1, F(000) = 532, the final R = 0.0372 and wR = 0.0930 for 1926 observed reflections with I＞2σ(I). The central zinc atom is five-coordinated in a distorted square pyramidal environment to three oxygen atoms of two different maleate ligands, a nitrogen atom of the imidazole ligand and an oxygen atom of water. In the complex two carboxylate groups of the maleate ligands have two coordination modes. One acts as a bidentate chelate ligand and the other a monoatomic monodentate ligand to bridge two zinc centers. As a result, 1-D infinite polymeric coordination water OH groups and carboxylate oxygen atoms to construct a 2-D layered polymer,and the layer structure is stabilized by π-π stacking of the imidozel ligands.     

Synthesis and Structure of Bis-( o-vanillin)di pyridine Nickel(Ⅱ)-pyridine Dihydrate

1　ＩＮＴＲＯＤＵＣＴＩＯＮＴｈｅｍｉｘｅｄｃｈａｌｅｔＮｉ(Ⅱ)ｃｏｍｐｌｅｘｅｓｃｏｎｔａｉｎｉｎｇｐｙｒｉｄｉｎｅｓｈａｖｅｂｅｅｎｏｆｇｒｅａｔｉｎｔｅｒｅｓｔｆｏｒｉｎｏｒｇａｎｉｃａｎｄｂｉｏｉｎｏｒｇａｎｉｃｃｈｅｍｉｓｔｓ[1～5].ＶａｎｉｌｌｉｎｉｓｏｎｅｏｆｔｈｅｎｏｒｍａｌｕｓｅｄｃｏｍｐｏｕｎｄｓｗｈｉｃｈｈａｖｅｔｗｏｏｘｙｇｅｎａｔｏｍｓａｎｄａｒｅｅａｓｙｔｏｆｏｒｍａｎｕｍｂｅｒｏｆｃｏｍｐｌｅｘｅｓｗｉｔｈＣｕ(Ⅱ),Ｃｏ(Ⅱ),Ｎｉ(Ⅱ),Ｚｎ(Ⅱ)ａｎｄｅｔａｌ[6].Ｉｎｔｈ…