混合配体的铜(Ⅱ)配合［Cu(C2H4O2N)(C12H8N2)(H2O)］.ClO4.2.5H2O的合成、性质及晶体结构

本文对甘氨酸、1,10-邻菲咯啉铜(Ⅱ)固体配合物进行了合成和表征,并利用X射线分析研究了其晶体结构。     

配合物[Cu2(C4H2O6)(Phen)2(H2O)]·8H2O的合成、晶体结构和抗菌活性

在pH≈10的乙醇-水溶液中以硫酸铜、酒石酸和邻菲咯啉反应合成了分子式为[Cu₂(C₄H₂O₆)(Phen)₂(H₂O)]·8H₂O的配合物单晶。用X-射线单晶衍射测定了晶体结构，并研究了配合物对大肠杆菌、金黄色葡萄球菌、枯草杆菌的抗菌活性。晶体属单斜晶系，空间群P2₁。标题化合物为双核铜配合物，2个铜原子配位数不同。Cu(1)是五配位的，具有扭曲的四方锥结构，5个配位原子分别是酒石酸的去质子的羟基氧和羧基氧、邻菲咯啉的2个氮原子及1个水分子的氧原子。Cu(2)为四配位的，配位原子分别是酒石酸的去质子的羟基氧和羧基氧和邻菲咯啉的2个氮原子。分子中Cu(1)…Cu(2)间的距离为0.354 8 nm。存在分子内邻菲咯啉-邻菲咯啉的面—面π-π相互作用，面间距为0.381 3 nm。配合物对大肠杆菌、金黄色葡萄球菌、枯草杆菌具有较强的抗菌活性。     

[Ag(4，4′-bpy)]+及[Zn(phen)2(H2O)2]2+两种配合物的合成、结构与荧光性质

用水热法和溶液法分别合成了2个新的配合物{[Ag(4,4′-bpy)]·3-HSBA.H2O}n(1)和[Zn(phen)2(H2O)2]·(A-2,5-DSA)·3H2O(2)(3-HSBA=3-羧基苯磺酸根,A-2,5-DSA=苯氨-2,5-二磺酸根,4,4′-bpy=4,4′-联吡啶,phen=1,10-邻菲咯啉),用X-射线单晶衍射结构分析方法测定了其晶体结构。配合物1是一维链状结构。在1个不对称单元中包含1个[Ag(4,4′-bpy)]+阳离子,1个3-羧基苯磺酸根阴离子和1个晶格水分子。Ag髣离子与2个4,4′-联吡啶的2个氮原子配位。配合物2是单核结构。在1个不对称单元中包含1个[Zn(phen)2(H2O)2]2+阳离子,1个苯氨-2,5-二磺酸根阴离子和3个晶格水分子。Zn髤离子与2个1,10-邻菲咯啉的4个氮原子和2个水氧原子配位。配合物1和2中,配位阳离子、抗衡阴离子以及晶格水分子之间存在丰富的氢键,进而构筑成超分子网络结构。配合物的荧光均来自于配体的π-π*电子跃迁。     

双核配合物[Cu2(L-Asp)(phen)3(NO3)](NO3)·4H2O的合成及晶体结构

The new complex [Cu₂(L-Asp)(phen)₃(NO₃)](NO₃)·4H₂O (L-Asp=L-aspartic acid and phen=1,10-phenanthroline) has been synthesized and its crystal structure has been determined. The complex crystallizes in the monoclinic with space group P2₁/c, The cell parameters are: a=1.261 3(2) nm, b=1.500 8(4) nm, c=2.230 7(4) nm, β=99.55(1)°, and V=4.164 1(16) nm³，D_c=1.587 g·cm^-3. The complex contains two six-coordinated copper ions, and these two copper ions are connected together by L-aspartate to give rise to a binuclear structure. Hydrogen bonds and π-π stacking interactions are observed in the complex. CCDC: 249250.     

[Mn(H2O)(phen)2(PAc)](ClO4)的合成、红外光谱及晶体结构

The complex [Mn(H₂O)(phen)₂(PAc)](ClO₄) was synthesized and investigated by elemental analysis, molar conductivity, IR spectrum and X-ray diffraction methods, where phen=1,10-phenanthroline and PAc=phenylac-etate group. The complex crystallizes in the triclinic space group,P1 , with a=0.9289(2)nm,b=1.2425(2)nm,c=1.4791(3)nm,α=114.34(3)°,β=91.25(3)°,γ=104.65(1)°,V=1.4893(4)nm³,Z=2,F(000)=686,D_c=1.489g·cm^-3,μ=0.589mm^-1. The Mn(Ⅱ) ion has a six-coordinate distorted-octahedral geometry with the four nitrogen atoms of two phen ligands,a coordinated-water oxygen atom, and a carboxylate oxygen atom of PAc^-. There is π-π stacking interaction between two phen rings from two neighbor molecules.     

配合物[Cu(H2O)(C12H8N2)2]·2ClO4的合成、性质及晶体结构

合成了配合物 [Cu(H2 O) (C12 H8N2 ) 2 ]·2ClO4 (C12 H8N2 为 1,10 邻菲咯啉 ) ,用元素分析、摩尔电导、红外光谱及电子光谱进行了表征 ,并测定了配合物的晶体结构。该晶体属单斜晶系 ,空间群为CC;晶胞参数 :a =1.9177(2 )nm ,b =0 .81994(0 )nm ,c=1.6 2 45 8(14)nm ,β =10 0 .10 4(6 )° ;V =2 .5 419(4)nm3,Z =4,F(0 0 0 ) =130 0 ,DC=1.6 93g/cm3,R =0 .0 430 ,wR =0 .1195。中心铜 (Ⅱ )离子与两个 1,10 邻菲咯啉的四个N原子和一个水分子的氧原子配位 ,形成了一个变形的三角双锥结构     

配合物[La(pic)3(phen)2]·CH3CN的合成及晶体结构

The Lanthanum picrate complex with 1,10-phenanthroline was synthesized, whose chemical formula can be written in [La(pic)₃(phen)₂]·CH₃CN. The crystal Xray diffraction analysis shows that crystal belongs to monoclinic with space group P2₁/a and unit cell parameters:a=17.072(4),b=16.083(4),c=17.789(4),β=106.34(2)°,V=4687(4)³, Z=4,Dc=1.735g·cm³, μ=10.106cm¹,F(000)=2448,R=0.0589,Rw=0.0589. The coordination number of La³⁺ is nine. Acetonitrile, a solvent molecule is not coordinated. Between three Pic ligands, that possesses 2 bidentate forms six member ring with La. The other is unidentate ligand. As usually, phen is bidentate ligand.     

配合物[Cu(m-TFBA)(phen)(H2O)2]·(m-TFBA)的水热合成、晶体结构及量子化学研究

以醋酸铜、间三氟甲基苯甲酸(m-TFBA)和邻菲咯啉(phen)为原料在甲醇水介质中通过水热反应,合成了一个新的单核 铜?髤配合物[Cu(m-TFBA)(phen)(H₂O)₂]·(m-TFBA),用元素分析、红外光谱和热重分析对配合物进行了表征。X-射线单晶衍射表明,配合物属三斜晶系,空间群P1,晶胞参数：a=1.001 61(10) nm,b=1.150 69(12) nm,c=1.286 49(12) nm,α=82.217(2)°,β=84.767(2)°,γ=66.371(2)°,V=1.344 8(2) nm³,Z=2,D_c=1.625 g·cm^-3,R₁[I>2σ(I)]=0.042 1,wR₂[I>2σ(I)]=0.095 8。铜(Ⅱ)分别与来自邻菲咯啉的2个氮原子、间三氟甲基苯甲酸的1个氧原子和2个水分子中的2个氧原子配位,形成变形的四方锥结构。配合物通过强的O-H…O氢键作用形成了二聚体结构,该二聚体又通过分子间弱的C-H…O氢键作用形成了一维链状结构。配合物中配位的间三氟甲基苯甲酸上的三氟甲基基团具有无序结构。对配合物中[Cu(m-TFBA)(phen)(H₂O)₂]⁺进行了量子化学从头计算,探讨了配合物的稳定性、分子轨道能量以及一些前沿分子轨道的组成特征。     

配合物[Mn(phendione)(PDC)(H2O)2]·2H2O的合成与晶体结构

The title compound [Mn(phendione)(PDC)(H₂O)₂]·2H₂O (H₂PDC=pyridine-2，6-dicarboxylic acid) has been prepared in aqueous solution and characterized by single X-ray diffraction structure determination， elemental analysis， IR spectroscopy， and thermal analyses. The compound crystallizes in Monoclinic system， space group C2/c， a=1.017 51(11) nm， b=1.483 25(11) nm， c=1.461 21(13) nm， β=109.86(10)°， V=2.074 1(3) nm³， Z=4， F(000)=1 028， μ=0.701 mm^-1， D_c=1.609 g·cm^-3， R₁=0.028 9， wR₂=0.078 8 [I>2σ(I)]. Crystal structure reveals that complex consists of one-dimensional chain framework bridged by hydrogen bonds that formed by uncoordinated water and oxygen atom of carboxyl group in PDC^2-. Furthermore， the complexes form a three-dimensional super-molecular structure through hydrogen bonds. CCDC: 648570.     

基于L-O-磷酸丝氨酸配合物[Cu(OPSer)(phen)(H2O)]·3H2O的合成、结构和性质

合成了铜(Ⅱ)的手性单核配合物[Cu(OPSer)(phen)(H2O)]·3H2O(1)(H2OPSer=L-O-磷酸丝氨酸;phen=1,10-邻菲啰啉)。通过元素分析、红外光谱、热重分析和磁性对配合物进行表征,并利用单晶X-射线衍射法测定其结构。铜(Ⅱ)具有变形四方锥的配位环境,分别与1个L-O-磷酸丝氨酸离子的1个氮原子和氧原子、1个1,10-邻菲啰啉分子的2个氮原子以及1个配位水分子的氧原子配位。配合物每个分子单元通过氢键连接成三维超分子结构,分子间存在π-π堆积作用。在1.8~300 K范围内磁性测定表明:配合物1中存在铁磁耦合相互作用,经理论拟合:g=2.07,zJ′=0.044。     

用T-jump/FTIR研究MnCP、NiCP和PbCP的快速热分解(英)

0IntroductionCarbohydrazideisahydrazinederivativewithwhitecrystalofstrongreducingbehaviors.Becauseithasmanycoordinationatoms(fournitrogenatomsandoneoxygenatom),carbohydrazidecan,therefore,beusedasmultidentateligand.Itscoordinationcom鄄poundiswidelyusedint…     

Synthesis and characterization of the [Cu(Cin2bda)2]ClO4 and [Cu(Ncin2bda)2]ClO4 complexes: Crystal structure of [Cu(Ncin2bda)2]ClO4

Two copper(I) complexes [Cu(Cin₂bda)₂]ClO₄ (I) and [Cu(Ncin₂bda)₂]ClO₄ (II) have been prepared by the reaction of the ligands N²,N²′-bis(3-phenylallylidene)biphenyl-2,2′-diamine (L¹) and N²,N²′-bis[3-(2-nitrophenyl)allylidene]biphenyl-2,2′-diamine (L²) and copper(I) salt. These compounds were characterized by CHN analyses, ¹H NMR, IR, and UV-Vis spectroscopy. The C=N stretching frequency in the copper(I) complexes shows a shift to a lower frequency relative to the free ligand due to the coordination of the nitrogen atoms. The crystal and molecular structure of II was determined by X-ray single-crystal crystallography. The coordination polyhedron about the copper(I) center in the complex is best described as a distorted tetrahedron. A quasireversible redox behavior was observed for complexes I and II. The article is published in the original.     

Non-equivalent water molecules in [Ni(H2O)6](ClO4)2 and in [Ni(D2O)6](ClO4)2 in the thermogravimetric investigations

The thermal decomposition of [Ni(H₂O)₆](ClO₄)₂ and [Ni(D₂O)₆](ClO₄)₂ were studied by thermogravimetric analysis (TG) and simultaneous differential thermal analysis (SDTA) at a constant heating rate. The gaseous products of the decomposition were on-line identified by a quadrupole mass spectrometer (QMS). In both cases the process of decomposition starts at ca. 410 K and is connected with removal of water molecules in a stepwise way; at the beginning the first water molecule is lost, then the second and at higher temperature the third one. The rest of the water molecules are lost in the temperature region of ClO₄⁻ decomposition. The energy of activation of the process was calculated in both cases.     

[COH(NH2)2]2[Cu(pic)2(ClO4)2]的合成与晶体结构

The title compound was synthesized by reaction of Cu(ClO₄)₂， picolinic acid and carbamide in C₂H₅OH/CH₃CN solution， and characterized by single-crystal X-ray diffraction. It crystallizes in the orthorhombic system， space group Pbca with a=14.0481(8)， b=9.0130(5)， c=18.626(1)?， V=2358.3(2)?³， Z=4， D_x=1.771g·cm^-3， μ=1.235mm^-1 and F(000)=1276. The final R factor is 0.0440 for 1434 observed reflections. The X-ray analysis revealed that the copper(Ⅱ) atom is coordinated by two picolinic ligands in the equatorial plane， while the two oxygen atoms of perchlorate occupy the axial positions of octahedron with lengthened Cu-O distances， resulting in a 4+2 elongated octahedral environment. In the compound， there also exist two protonated carbamide cations for charge balance. CCDC： 195354.     

Neutronenstreuungsuntersuchungen an UO2(ClO4)2-L?sungen

Ohne Zusammenfassung     

二维网状配合物[Co(dimb)2(MeOH)2](ClO4)2的合成及晶体结构

设计并合成了一个含咪唑基团的柔性双齿配体:1,3-二(咪唑基-1′-甲基)-5-甲基苯(dimb)(1),并进行了 ¹H NMR和结构表征。通过dimb与高氯酸钴的反应,得到了一个新型的具有二维网状结构的配合物:[Co(dimb)₂(MeOH)₂](ClO₄)₂(2)。X-射线晶体结构测定表明,这两个化合物的晶体学参数分别为:配体(1)属单斜晶系, 空间群     

A novel three-dimensional malonate-bridged complex {[Cu4(4,4′- bpy)8(mal)2(H2O)4](ClO4)2(H2O)4(CH3OH)2}n

A novel malonate-bridged copper (II) compound of formula {[Cu₄(4,4′-bpy)₈(mal)₂(H₂O)₄](ClO₄)₂(H₂O)₄(CH₃OH)₂}_n (4,4′-bpy = 4,4′-bipyridine; mal = malonate dianion) has been prepared and structurally characterized by X-ray crystallography. This compound exhibits a novel three-dimensional network being composed of Cu-4,4′-bipyridine layers which are pillared by malonate bridge ligands. The copper(II) ions has two different coordination environment.     

配合物[Mn(bipy)3](ClO4)2的晶体结构和热分析研究

The complex [Mn(bipy)₃]·(ClO₄)₂ was synthesied and characterized by X-ray diffraction. X-ray diffraction result for the single crystal showed that the crystal belongs to triclinic, space group P1, a=0.8123(2),b=1.1024(2), c=1.8646(4)nm,α=102.30(3)°,β=91.00(3)°,γ=99.69(3)°,V=1.6056(6)nm³,Z=2,D_c=1.494g·cm^-3. The thermal decomposition of [Mn(bipy)₃](ClO₄)₂ occurred in a three steps pattern. The reaction mechanism of the first step decomposition was deduced as n(1-α)[-ln(1-α)](n-1)/n with the activation energy of 130kJ·mol^-1.     

Complexes of N,N′,N′′-tris(2-hydroxypropyl)-1,4,7-triazacyclononane (L): Structures of [CuL](ClO4)(NO3), [CoL](ClO4)2, [ZnL](ClO4)2 and the catalytic activity of [MnL](ClO4)2 towards olefin epoxidation with hydrogen peroxide

Complexes of N,N′,N′′-tris(2-hydroxypropyl)-1,4,7-triazacyclononane (L), [CuL](ClO₄)(NO₃) (1), [CoL](ClO₄)₂ (2), [ZnL](ClO₄)₂ (3) and [MnL](ClO₄)₂ (4), have been synthesized and characterized on the basis of elemental analysis, electrospray ionization mass spectrometry, UV–Vis measurements and cyclic voltammetry. Crystal structures of the former three complexes, characterized by X-ray crystallography, show that these complexes are monoclinic with space group P2₁/n and P2₁/c. Each metal central in the complexes is six-coordinate with three N atoms of the macrocycle and three O atoms from the pendant hydroxypropyl arms, forming a distorted octahedral configuration. [MnL](ClO₄)₂ (4) is employed as catalyst in olefin epoxidation with H₂O₂. The final results indicate that complex (4) has good catalytic activity towards olefin epoxidation. Under mild conditions, the olefin conversion is moderate and epoxidation selectivity is 95–100%.     

[Gd2(Gly)6(H2O)4](ClO4)6(H2O)5的合成、晶体结构与热化学研究

利用微波技术合成了配合物[Gd₂(Gly)₆(H₂O)₄](ClO₄)₆(H₂O)₅, 进行了化学成分分析、红外表征和热重分析. 应用X衍射仪测定其晶体结构, 该晶体为一维链结构, 属三斜晶系, P 空间群, 晶胞参数: a＝1.1569(17) nm, b＝1.4138(2) nm, c＝1.5642(2) nm, α＝96.910(2)°, β＝102.735(2)°, γ＝105.512(2)°, V＝2.3606(6) nm³, Z＝2, D_c＝2.144 g•cm^－3. 采用精密溶解-反应量热计, 通过设计热化学循环, 计算出了该配合物的标准摩尔生成焓为 －(7960.73±3.23) kJ•mol^－1.