SYNTHESIS AND STRUCTURE OF CU8S[S2P（OC2H5）2]6

<正> Cu8C24H60O12P6S13,Mt= 1651. 73,trigonal,R3,a=b = c= 12. 667(4) A,α= β=γ=111. 42(1)°.V=1441(2)A3,Z=1,Dc=1. 903g·cm-3,λ(MoKa) = 0. 71073 A ,μ(MoKa) = 35. 671cm-1, F ( 000 ) = 830, 293K. Final R = 0. 066,Rw= 0. 077 for 850 unique intensity data (I≥3σ(I)). Each unit cell of the crystal comprises of a neutral molecule of formula Cu8S(dtp)6[dtp=S2P(OEt)2],wherein the eight copper atoms are arranged at the corners of regular cube,with each dtp ligand μ4-bridged to each face of the cube and a μ8-S in the center bonded to all the eight copper atoms. Each copper atom is coordinated by four sulfur atoms in a tetrahedral configuration. The bond lengths of Cu-(μ8-S) are in the range of 2. 627(2)-2. 543(2) A ,those of Cu-S(dtp)in the range of 2. 251-2. 280A.The adjacent Cu-Cu bond lengths (2. 950(5)-3. 070(2) A) show a weak interaction between the copper atoms     

Crystal Structure and Properties of a Copper(Ⅱ) Complex Containing p-Toluenesulfonate and Imidazole Ligands

A novel supramolecular mixed ligand complex of formula [Cu(PTS)2(Him)2(H2O)2] (C20H26CuN4O8S2,PTS=p-toluenesulfonate,Him=imidazole) has been synthesized in aqueous solution and characterized by elemental analysis,IR and single-crystal X-ray diffraction.The compound crystallizes in the monoclinic system,space group P21/n,Z=2,a=5.650(2),b=14.671(3),c=14.638(3),β=100.10(3)°,V=1194.60(4)3,Dc=1.607 g/cm3,μ(MoKα)=1.143 mm-1,F(000)=598,R=0.0615 and wR=0.1503 for 1752 observed reflections with I 2σ(I).The copper(II) ion in the complex adopts a slightly distorted octahedral coordination geometry and is six-coordinated with N2O4 donor set consisting of two nitrogen atoms and four oxygen atoms provided by the ligands of two imidazole molecules,two water molecules and two p-toluenesulfonate ions.The sulfonate group of the PTS ligand remains weak-coordinated and forms a number of hydrogen bonds with water molecules and imidazole ligands.X-ray structural analysis reveals that the coordination molecules are connected to form a 3-D supramolecular framework by electrostatic interaction,weak van der Waals forces,hydrogen bonding and π-π interaction.The thermal behaviour of the title complex was investigated by using DSC and TG-DTG techniques.     

Photovoltaic Characteristics of a Naphthylamine Derivative

Organic photovoltaic （OPV） cells were fabricated via vacuum vapor deposition with {4-[2-（3-di-cyanomethylidene-5,5-dimethylcyclohexenyl）vinyl]phenyl}di（1-naphthyl）amine （DNP-2CN） as the electron donor, and fullerene （C60） as the electron acceptor. A thin film （10 nm） of tris（8-quinolinolato）aluminum （Alq3） was adopted as the buffer layer. A device based on this DNP-2CN exhibited an open circuit voltage （Voc） of 370 mV, a short-circuit current density （Jsc） of 0.61 mAocm 2, and a white-light power conversion efficiency （ η） of 0.09% （AM1.5, 75 mW.cm^- 2）.     

Synthesis, Structure and Magnetic Properties of a Linear Trinuclear Mn（II） Complex with a Multifunctional Group Ligand

By use of a new ligand containing both salicylic acid moiety and salicylaldehyde Schiff base moiety, 5-(2-hydroxybenzylideneamino)-2-hydroxybenzoic acid (H3L), a linear trinuclear Mn(II) complex was prepared. This complex crystallizes in triclinic, space group P1 with a = 12.0196(7), b = 13.7440(13), c = 15.7554(14) , α = 111.529(3), β = 96.691(2), γ = 94.802(2)o, C96H100Mn3N6O32, Mr = 2014.64, V = 2382.0(3) 3, Z = 1, μ = 0.478, Dc = 1.404 g/cm3, F(000) = 1049, R = 0.0554 and wR = 0.1610 for 8973 observed reflections (I 2σ(I)). The complex consists of a trinuclear cluster and two solvate ethanol molecules. Three linearly disposed Mn atoms, with an inversion center on the central one, are bridged by six carboxylate groups from six bulky mono-anionic ligands (H2L–), and the octahedral coordination spheres for each of the metal centers are thus formed, with the aid of additional ligation of two small molecules (ethanol and water) to both ends. The magnetic properties of the title complex are also included in this paper.     

Synthesis, Crystal Structure and Photoluminescence of a 2D Two-fold Interpenetrating Cd(Ⅱ) Coordination Polymer Based on a Flexible Reduced Schiff Base Ligand

<正>By the reaction of cadmium chloride with a reduced Schiff base ligand (H_2L = N-(4- carboxybenzyl)-glycine), a novel Cd(II) compound [Cd(HL)_2]·4H_2O (1) has been obtained. Single-crystal X-ray diffraction analysis reveals that it crystallizes in orthorhombic, space group Pbcn with a = 13.9788(8), b = 24.4204(14), c = 13.9580(8), V = 4764.8(5)~3, Z = 8, M_r = 600.84, D_c = 1.675 g/cm~3, μ = 0.983 mm~(-1), F(000) = 2448, S = 1.084, R = 0.0806 and wR = 0.1705 (I > 2σ(I)). It displays a 2D two-fold interpenetrating structure. The Cd(II) ions are six-coordinated. The cross-linkage of Cd(II) ions by the bridge of HL anions results in a [Cd(HL)_2] layer. Every two [Cd(HL)_2]_n layers are penetrated with each other, resulting in a two-fold interpenetrating double-layer structure by π-π stacking interactions and hydrogen bonds. Such double-layers are further linked by hydrogen bonds into a supramolecular structure. Photoluminescent investigation shows that compound 1 displays strong emission in the purple region.     

Synthesis and Crystal Structure of a New Diamine Complex CuC14（H2tn）

In an attempt to synthesize a new pyrimidine complex of copper(H) in a solution reaction of CuBr2 with 2,2‘-bis(hexahydropydmidine) and hydro-chloric acid, we unexpectedly obtained a bright yellow chip-like crystal of CuCl4(H2tn) [H2tn=(H3NCH2CH2CH2NH3)^2 ]. Its structure was determined by single-crystal X-ray diffraction analysis. The crystal belongs to orthorhombic system, space group Pnma, with cell parameters: a=0.7216(2)nm, b=1.8308(6)nm, c=0.7553(3)nm, V=0.9953(6)nm^3, Z=4, F(000)=564, Mr=281.49, Dc=1.879 g/cm^3. u(Mo Ka)=3.204 mm^-1, R1=0.0248, wR2=0.0575. The analysis of the crystal structure indicates that the complex has a three-dimensional network structure, which is formed by hydrogen bonds and electrostatic interaction.     

Activation of Nitromethane to Cyanide by a Mononuclear Cu(Ⅱ) Complex

The tridentate ligand DPA-Me(2) was readily prepared from DPA(DPA = 2,2-dipicolylamine) in high yield. The mixture of 2 and Cu(Cl O4)26H2O in methanol gave a five-coordinated mononuclear complex [(DPA-Me)Cu(Me CN)(Cl O4)](Cl O4)(3). Recrystallization of 3 in CH3NO2 led to an activation of CH3NO2 to CN- by the formation of product as a dinuclear cyanide bridged complex {[Cu(DPA-Me)]2(CN)(Cl O4)3CH3NO2}n(4). Both 3 and 4 were characterized by X-ray crystallography, IR spectroscopy and elemental analysis. The crystal of 4 was grown in space group P21/c with a = 17.74582(15), b = 13.89877(11), c = 14.92546(13) , β = 91.4246(8)°, V = 3680.15(5) 3, Z = 4, Dc = 1.695 g/cm3, F(000) = 1912, C28H33Cl3Cu2N8O14, Mr = 939.05, μ = 1.602 cm-1, Cu Kα radiation(λ = 1.54184 ), R = 0.0485 and w R = 0.1246 for 6414 observed reflections with I 2σ(I).     

Synthesis, Crystal Structure and Antibacterial Activity of a New Ternary Copper（Ⅱ） Complex with 2,6-Pyridinedicarboxylic Acid and 1,10-Phenanthroline

A new ternary copper(II) complex,[C 43 H 27 Cu 2 N 7 O 5 ]·[C 14 H 6 CuN 2 O 8 ]·6.5H 2 O,has been synthesized by the reaction of copper sulfate,2,6-pyridinedicarboxylic acid and 1,10-phenanthroline (phen),and characterized by elemental analysis,IR,UV and X-ray single-crystal diffraction.It crystallizes in triclinic,space group P1,with a=14.379(5),b=15.510(5),c=15.835(6),α=78.567(6),β=63.594(6),γ=81.287(6)°,V=3092.1(19)3,C 57 H 46 Cu 3 N 9 O 19.5,M r=1359.54,Z=2,D c=1.446 Mg/m 3,λ(MoKα)=0.71073,μ=1.101 mm-1,F(000)=1362,S=1.071,the final R=0.0718 and wR=0.11960 for 10705 observer reflections (I > 2σ(I)).The structure unit of the title complex consists of a mononuclear part and a di-nuclear part,and the three copper ions show three coordination modes.Each 6-coordinated geometry of the Cu atom is a distorted octahedral coordination geometry.The 3D supramolecular system is formed by the hydrogen bond O-H···O and π-π stacking interaction between neighboring single cells.The antibacterial activity of the title complex is also studied.     

Synthesis and Crystal Structure of a Two—dimensional Polymeric Holmium

The title polymeric complex [Ho(H2saln)1.5(NO3)3](H2saln=N,N'-bissalicyclidene-ethylenediamine) C24H24N6O12Ho was prepared and its crystal was characterized by X-ray diffraction. The ligand is dischiff base from salicylaldehyde and ethylenediamine. The complex crystallizes in trigonal system, space group Pc1(No. 165), Mr=753.42, a=15.818(2), c=16.978(3) , V=3681(2) 3, Dx=1.360 g/cm3, Z=4, μ=2.2286 mm-1, F(000)=1492, R=0.049, Rw=0.061. In the complex the coordination number of Ho(Ⅲ) is 9 with the geometry of a tricapped trigonal prism. All of the coordination atoms are oxygen atoms. The Ho(Ⅲ) ions are bridged by the dischiff base to form an infinite two-dimensional polymeric network, parellel to the (001) plane.     

Hydrothermal Synthesis and Structural Characterization of a Novel Organic—Inorganic Hybrid Compound {[Cu（2,2′—bpy）2]2—Mo8O26}

A novel organic-inorganic hybrid compound {[Cu(2,2′-bpy)2]2Mo8O26} has been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction. The compound crystallizes in the orthorhombic space group, Pna21,with a=2.4164(5),b=1.8281(4),c=1.1877(2)nm,V=5.247(2)nm^3,Z=4,and final R1=0.0331,wR2=0.0727.The structure consists of discrete {[Cu(2,2′-bpy)2]2Mo8O26} clusters,constructed from a β-octamolybdate subunit[Mo8O26]^4- covalently bonded to two [Cu(2,2′-bpy)2]^2 coordination complex cations via bridging oxo groups.In addition,the spectroscopic properties and thernal behavior of this compound have been investigated by spectroscopic techniques (UV-vis,IR,Raman and EPR spectra) and TG analysis.     

Effects of systematic methyl substitution of metal (III) tris(n-methyl-8-quinolinolato) chelates on material properties for optimum electroluminescence device performance.

We relate the chemical structure of a series of methyl (Me) substituted group III metal tris(8-quinolinolato) chelates (nMeq(3)M: n = 0, 3, 4, 5; M = Al(3+), Ga(3+)) to their photoluminescence (PL), electroluminescence, and thermal properties. Methylation of the 8-quinolinol ligand at the 3 or 4 position (pyridyl ring) results in a factor of 1.4 and 3.0 enhancement of PL quantum efficiency (phi(PL)), respectively, whereas methylation at the 5 position (phenoxide ring) results in a factor of approximately 3.0 decrease in phi(PL) relative to the unsubstituted analogue. Electroluminescent quantum efficiencies of undoped organic light-emitting devices using the aluminum tris(8-quinolinolato) chelates are 1, 0.45, 1.4, and 0.80% for unsubstituted 5-, 4-, and 3-methyl-8-quinolinol ligands, respectively. Devices made with the latter two ligands have a higher operating voltage to generate the same current density. Similar trends were observed for methylation of gallium tris(8-quinolinolato) chelates. We relate these results to the thermal properties of the compounds measured by simultaneous differential scanning calorimetry and thermal gravimetric analysis. The C-4 methylated derivatives exhibit approximately 60 degrees C lower crystalline melting points than all other derivatives, indicating the weakest cohesive forces between molecules. Unlike Alq(3), both the C-4 and C-5 methylated derivatives show no recrystallization of the glassy state below 500 degrees C and exhibit approximately 20-25 degrees C higher glass transition temperatures. We infer that methylation of the 8-quinolinol ligand reduces intermolecular interactions and consequently impedes charge transport through the film.     

The 1H NMR spectra of 8-quinolinolato complexes of Mn(III)

¹H NMR spectra are reported for tris(8-quinolinolato)manganese(III), tris(2-methyl-8-quinolinolato)manganese(III) and mixtures of tris(acetylacetonato)manganese(III) and tris(8-quinolinolato)manganese(III). In the latter case, mixed complexes are formed in equilibrium, with only one of the three possible isomers of acetylacetonato bis(8-quinolinolato)manganese(III) being present in detectable amounts. The spectra were assigned making extensive use of selective deuteriation.     

Base hydrolysis of halobis/8-quinolinolato/ oxotechnetium/V/ complexes

Reaction mechanism of base hydrolysis of halobis/8-quinolinolato/oxotechnetium (V) /TcOX (ox)₂ X=Cl and Br/ was investigated by means of solvent extraction and spectrophotometric methods. Furthermore, distribution coefficients of tris/acetylacetonato/technetium/III/, dichlorobis/8-quinolinolato/technetium/IV/ and TcOX/ox/₂ between chloroform and aqueous solutions were determined. In an alkaline solution, TcOX/ox/₂ decomposed to pertechnetate as a final product. On the basis of the established base hydrolysis, the respective rate constants were determined.     

X-Ray Structure of 8-Quinolinolato Lanthanide Complex: (8-Quinolinolato)bis(2,6-di-tert-butyl-4-methylphenoxo)samarium

Ｉｎｔｒｏｄｕｃｔｉｏｎ8 Ｈｙｄｒｏｘｙｑｕｉｎｏｌｉｎｅｉｓａｃｌａｓｓｉｃａｌｃｈｅｌａｔｉｎｇａｇｅｎｔｆｏｒｔｒａｎｓｉｔｉｏｎｍｅｔａｌｓａｎｄｌａｎｔｈａｎｉｄｅｓ .Ｒｅｃｅｎｔｌｙｍｅｔａｌｃｏｍ ｐｌｅｘｅｓｉｎｃｏｒｐｏｒａｔｉｎｇ 8 ｑｕｉｎｏｌｉｎｏｌａｔｏｌｉｇａｎｄｓｈａｖｅｒｅｃｅｉｖｅｄｍｏｒｅａｎｄｍｏｒｅａｔｔｅｎｔｉｏｎ .Ｔｈｅｒｅｓｅａｒｃｈｉｎｔｅｒｅｓｔｐｒｏｂａｂｌｙａｒｉｓｅｓｆｒｏｍｔｗｏａｓｐｅｃｔｓ .Ｆｉｒｓｔ,8 ｑｕｉｎｏｌｉｎｏｌａｔｏｍｅｔ…     

Synthesis, crystal structure, and luminescent properties of a binuclear gallium complex with mixed ligands

By introducing tridentate Schiff base ligands, a binuclear gallium complex with mixed ligands, bis(salicylidene-o-aminophenolato)-bis(8-quinolinolato)-bis-gallium(III) [Ga(2)(saph)(2)q(2)], has been synthesized and structurally characterized by single-crystal X-ray crystallography. Crystal data for C(44)H(30)Ga(2)N(4)O(6) are as follows: space group, triclinic, P; a = 11.357(3) A, b = 12.945(3) A, c = 12.947(3) A, alpha = 103.461(15) degrees, beta = 100.070(7) degrees, gamma = 96.107(18) degrees, Z = 2. This complex was identified as a dimeric complex of hexacoordinated gallium with strong intermolecular and intramolecular pi-pi stacking interactions between the pyridyl/pyridyl rings. The thermal analysis showed that Ga(2)(saph)(2)q(2) can readily form a stable amorphous glass with a high glass transition temperature (T(g) = 204 degrees C), which is 27 degrees C higher than that of tris(8-hydroxyquinolinolate)aluminum (Alq(3)). In addition, a high photoluminescence efficiency (phi(PL)) of 0.318 in DMF has been demonstrated, although the central gallium atom can result in heavy-atom quenching. Organic light-emitting diodes (OLEDs) based on this complex displayed a turn-on voltage as low as 2.5 V and a high efficiency. Even at a low doping concentration of 1%, the doped Ga(2)(saph)(2)q(2) devices with 4-(dicyanomethylene)-2-tert-butyl-6-(1,1,7,7-tetramethyljulolidyl-9-enyl)-4H-pyran (DCJTB) as the dopant exhibited excellent red emission centered at 628 nm with improved durability, compared with the case of Alq(3) as the host. These distinguishing properties of Ga(2)(saph)(2)q(2) make it a good candidate as a novel electron-transporting and emitting material for OLEDs.     

Tris(2-methyl-8-quinolinolato)iron(III) as a novel spectrophotometric probe for silanol detection.

Tris(2-methyl-8-quinolinolato)iron(III) was proposed as a sensitive spectrophotometric silanol-detecting probe based on the coordination ability of silanol groups on the surface of octadecylsylanized silica gel (ODS silica gel) for reversed-phase high-performance liquid chromatography. A peak of the iron(III) complex on a chromatogram abruptly collapsed as the silanol content in an ODS column increased, indicating that the iron(III) complex could sense trace amounts of silanol groups. The change of the peak parameters, such as the peak height and the peak area was highly related to the output of some nitrogen-containing compounds used as silanol-detecting probes as a function of the silanol content in an ODS column. The response of the peak height of the iron(III) complex to the silanol content was much more sensitive than the response of the nitrogen-containing probes, and was comparable to that of tris(2-methyl-8-quinolinolato)gallium(III), which had been proposed as a fluorometric silanol-detecting probe based on the coordination ability of the silanol groups.     

Synthesis and Crystal Structure of a Novel Cobalt（Ⅱ） Coordination Polymer with 1,2,4,5-Benzenetetracarboxylate

A novel cobalt（II） coordination polymer,[Co（BTEC）1/2]n 1,has been synthesized with Co（NO3）2·6H2O and 1,2,4,5-benzenetetracarboxylic acid （H4BTEC） by the hydrothermal method,and characterized by elemental analysis,IR and single-crystal X-ray diffraction. Crystallographic data for 1： C5HO4Co,Mr = 183.99,monoclinic,space group C2/c,a = 16.619（6）,b = 7.416（3）,c = 8.040（3）A,β = 90.612（4）°,V = 990.8（6） A^3,Z = 8,Dc = 2.467 g/cm^3,μ = 3.390 mm^-1,F（000） = 720,R = 0.0307 and wR = 0.0847 for 912 observed reflections （I 〉 2σ（I））. X-ray crystal structural analysis revealed that each Co（II） adopts a tetrahedral coordination mode to link four separate BTEC ligands via uniform monodentate carboxylate groups and each BTEC ligand possesses an 8-connected geometry to connect eight Co（II） ions. Complex 1 exhibits a rare （4,8）-connected net with （45.6）2（410.614.84） topology.     

Polymer-mediated extraction of 8-quinolinolato metal chelates for the determination of metal ions in water with graphite furnace atomic absorption spectrometry

Water-insoluble 8-quinolinolato metal chelates were formed and were stably solubilized in the aqueous solution of a water-soluble polymer, poly (N-isopropylacrylamide)(PNIPAAm), at room temperature. When the solution was heated at 50 degrees C, PNIPAAm precipitated and then formed a gum-like aggregate (polymer phase) having a very small volume. Accompanying the polymer precipitation, hydrophobic 8-quinolinolato chelates with cobalt(II), iron(III), nickel(II), and copper(II) ions were efficiently incorporated into the polymer phase. At 0.5% (w/v) of PNIPAAm and 8.0 mM of 8-quinolinol, the recoveries in the incorporation of four metal chelates were quantitative. The fluorescence spectra of a probe suggests that the hydrated polymer in the aqueous solution provides hydrophobic portions which can incorporate hydrophobic metal chelates. The polymer phase was easily taken out from the solution and was dissolved with a small amount of acetonitrile. The resulting solution could be directly introduced into a graphite furnace of atomic absorption spectrometry. The signal intensities for the absorbance of cobalt after concentrating the chelate were 100-fold greater than those before the concentration.     

新型环形聚阴离子[{WO(H_2O)}_3(AsW_8O31)_3]~21-的结构及表征

在pH=3.0的水溶液中，Na_2WO_4·2H_2O与NaAsO_2·6H_2O和NH_4Cl反应，得 到了新的杂多钨酸盐(MH_4)_19Na_2[{WO(H_2O)}_3(AsW_8O31)_3]·45H_2O单晶， 用X射线单晶衍射法及元素分析确定了其结构，晶体属单斜晶系，空间群C2/c，晶 胞参数为：a=3.1165(11)nm, b=1.7388(7)nm, c=2.2789(9)nm, β=97.342(6)°, V=12.248(8)nm~3, Z=4, R_1=0.0571,wR_2=0.0741[I＞2σ(I)]. 环型聚阴离子 [{WO(H_2O)}_3(AsW_8O31)_3]~21-是由三个{WO(H_2O)}桥连三个新发现的 {AsW_8O31}单元构成的，环聚离子[{WO(H_2O)}_3(AsW_8O31)_3]~21-具有近似D_ (3h)对称性。对该化合物还进行了~183W NMR, IR和TG表征。     

系列双核Ln(III)配合物的晶体结构和磁性

合成了分子式为[Ln~2(phen)~2L],phen=C~1~2H~8N~2[ALn=Nd,L=(CH~3COO)~4(ONO~2)~2,BLn=Sm,L=(C~6H~5COO)~6,CLn=Eu,L=(C~6H~5COO)~6]3种同双核配合物。用X射线四圆衍射仪测定了3种化合物的结构。在化合物A分子中,2个Nd(III)原子由4个CH~3COO^-基团桥联,以phen和ONO~2^-为端基,构成了一个具有C~2对称性的双核分子。配合物B和C具有完全相同的结构,它们是以4个苯甲酸根为桥,2个phen和2个C~6H~5COO^-为端基的中心对称双核分子,其中6个苯甲酸根的成键状态可分为3种状况。在3种化合物中,每个Ln均为9配位,呈不规则多面体。Ln-Ln距离,A为0.397nm,B和C均为0.405nm。测定了各配合物的变温磁化率,通过对磁性质研究,发现化合物A在低温下具有反铁磁物质行为,并由理论拟合,求得了磁参数g,J值。