配位聚合物[Cd2(BDC)2(obix)2]·H2O的合成、晶体结构和荧光性质

用水热合成方法得到1个新的配位聚合物[Cd2(BDC)2(obix)2]·H2O(H2BDC=对苯二甲酸,obix=1,2-(二亚甲基)二咪唑).配合物晶体属三斜晶系,P1空间群.晶体结构表明:镉原子与3个对苯二甲酸上的5个氧原子,2个1,2-(二亚甲基)二咪唑中的2个氮原子配位形成扭曲的五角双锥配位构型.2个Cd(Ⅱ)原子通过两个羧基桥联形成一个双核Cd2单元,再通过配体连接成二维层状结构,层与层之间通过C-H…O氢键和弱的π-π相互作用形成三维超分子结构.室温下配合物具有较强的荧光发射光谱.     

双核银配合物[Ag2(μ-(4-MeC6H4O)2PS2)2(Phen)2]的光谱性质和晶体结构

合成了双核银配合物[Ag2(μ-(4-MeC6H4O)2PS2)2(Phen)2](phen为1,10-邻菲咯啉),用元素分析、红外光谱、紫外-可见光谱和热重分析进行了表征,并用X-射线衍射法测定了晶体结构。该晶体属于正交晶系,Pbca空间群,晶胞参数为:a=1.2035(2)nm,b=1.638 3(3)nm,c=2.517 1(5)nm,V=4.963 1(17)nm 3,Dc=1.599 g.m-3,Z=4,F(000)=2 416,μ(Mo Kα)=1.072 mm-1,S=1.066,(Δ/σ)max=0.001,R1=0.037 6,wR2=0.088 8(I>2σ(I))。晶体结构研究表明每个Ag原子与不同配体(4-MeC6H4O)2PS2-的2个S原子和1个phen配体的2个N原子配位形成了具有椅式构型的八元环Ag2S4P2,Ag原子为畸变四面体AgS2N2构型,配合物通过phen的π-π堆积形成了一维结构,分子间的弱氢键C-H…O和C-H…π作用使分子进一步形成了三维网络结构。     

含能配合物[Mn(DAT)6](ClO4)2的合成、晶体结构、热行为及感度性质

合成了新型含能配合物[Mn(DAT)6](ClO4)2(DAT=1,5-二氨基四唑), 用X射线单晶衍射法测定了其晶体结构. 该晶体属三方晶系, P3c1空间群, a=b=1.18435(17) nm, c=1.3081(3) nm, α=β=90°, γ=120°, V=1.5891(5) nm3, Z=2. 该配合物分子结构单元中有1个Mn2+离子、6个DAT分子和2个ClO4-离子. 由6个DAT分子中的6个N原子与中心Mn2+离子配位形成六配位、非中心对称的畸变八面体结构. 利用元素分析、差示扫描量热分析(DSC)、热重-微分热重分析(TG-DTG)等方法进行了表征, 研究了其感度性能. 研究结果表明, 该配合物对外界刺激具有很高的响应性和危险性.     

铈配合物[Ce（4-aba）3（4-abaH）（phen）2]·H2O的合成与晶体结构

采用普通溶液法合成了单核铈配合物[Ce(4-aba)3(4-abaH)(phen)2]·H2O(4-abaH=对氨基苯甲酸,phen=1,10-邻菲罗啉)。X射线单晶衍射结果表明:该配合物晶体属单斜晶系,P21/c空间群,晶胞参数:a=1.8896(4)nm,b=1.9755(4)nm,c=1.3200(3)nm,β=97.235(2)°,V=4.8880(18)nm3,Mr=1064.06,Dc=1.446 g·cm-3,Z=4,μ=0.996 mm-1。中心铈离子的配位环境为变形的三帽三棱柱体。配合物存在着π-π堆积及丰富的氢键,将配合物扩展为三维超分子结构。     

二维层状铜配位聚合物[Cu2(TFBDC)2(DMF)2]2·3MeOH·2DMF的合成、晶体结构和磁性(TFBDC=四氟对苯二甲酸根；DMF=N，N-二甲基甲酰胺)

由Cu(Ⅱ)的硝酸盐与四氟对苯二甲酸(H2tfbdc)的自组装得到标题配合物.用元素分析、红外光谱、热重分析、X-衍射单晶结构分析等对其进行了表征.晶体结构表明,标题配合物的晶体属单斜晶系,空间群为C2/c,晶胞参数:a=3.3739(5)nm,b=1.5696(2)am,c=1.641 9(2)nm,β=1 17.527(2)°.每个铜离子与来自4个四氟对苯二甲酸分子的4个氧原子和1个N,N-二甲基甲酰胺分子中的氧原子配位,形成四方锥的配位构型.四氟对苯二甲酸根桥连铜离子形成具有孔穴的二维层状结构,相邻的层状结构又通过氢键形成三维的超分子网络结构.配合物中一些苯环上的-CF基团具有无序结构.变温磁化率数据(300～1.8 K)显示配合物中分别存在反铁磁性和铁磁性相互作用.     

三核铜(I/II)配合物[Cu(en)2][Cu(pht)2]2的合成、晶体结构及与DNA相互作用的研究

报道了多核铜配合物[Cu(en)2]•[Cu(pht)2]2 (Hpht: 苯妥英, 即5,5-二苯基-2,2-咪唑烷酮; en: 乙二胺)的溶剂热合成、晶体结构及其与DNA的相互作用. 该晶体属三斜晶系, Pī空间群, 晶胞参数: a＝0.8453(2) nm, b＝1.1878(3) nm, c＝1.5674(4) nm, α＝101.197(3)°, β＝97.690(3)°, γ＝103.283(3)°, V＝1.476(6) nm 3, Dc＝1.480 g/cm3, Z＝1, F(000)＝679, µ＝1.139 mm－1, R1＝0.0402, wR2＝0.0962[I＞2σ(I)], GOF＝1.035. XPS和X射线单晶衍射数据显示该配合物分子由混价铜组成, 包括两个一价铜和一个二价铜, 其中每个Cu(I)分别与两个苯妥英配体提供的氮原子配位, N—Cu(I)—N的夹角为177°, 一个Cu(II)与六个配位原子配位(CuN4O2), 形成一个稍变形八面体结构. 配合物与DNA相互作用研究表明, 该配合物主要是以插入方式与小牛胸腺DNA结合.     

配合物Zn(C3H4N2)2(C8H6O2Br)2的水热合成、晶体结构及性质

在140℃下,以3-溴-4-甲基苯甲酸和咪唑为配体,通过水热法在甲醇/水混合溶剂中反应24 h合成了锌(Ⅱ)配合物Zn(C3H4N2)2(C8H6O2Br)2。通过元素分析、红外光谱、热重分析和X射线粉末衍射对配合物进行了结构表征,同时用X射线单晶衍射分析确定了其晶体结构。结果表明,其晶体属单斜晶系,空间群为C2/c,晶胞参数:a=13.257(3),b=9.765(2),c=20.494(4),β=107.79(3)°,V=2526.3(9)3,Dc=1.655g·cm-3,μ=4.170mm-1,F(000)=1248,Z=4,最终残差因子R1=0.0552,wR2=0.1378。配合物为单核结构,中心锌(Ⅱ)离子与来自2个3-溴-4-甲基苯甲酸根的2个O原子及2个咪唑分子的2个N原子配位,形成了畸变的四方锥几何体。晶体内,分子间则通过N—H…O氢键作用在ab面形成了层状结构。研究了配合物的发光性质。     

配合物Fe(pda)2(H2O)4和[FeCo(pda)4(H2O)4]n的合成与晶体结构

采用水热法合成了2个3-(3-吡啶基)丙烯酸的配合物:Fe(pda)2(H2O)4(1)和[FeCo(pda)4(H2O)4]n(2)(pda=3-(3-吡啶基)丙烯酸),用红外光谱、元素分析、热重-差热以及X-射线衍射单晶结构分析进行了表征.2个配合物都属于单斜晶系,配合物1的空间群为P21/n,配合物2的为P21/c.配合物1是一个pda配体中仅吡啶基氮原子参与配位、而羧基上的氧原子未参与配位的单核结构,通过大量的氢键作用形成三维超分子体系.2是pda配体桥联Fe和Co的异核二维层状配位聚合物;配体吡啶基上的氮原子和羧基上的氧原子都参与了配位,其中羧基采用单齿配位模式.     

一维链状锌配位聚合物{[Zn(H2O)2(L)(phen)]·3H2O}n的合成、晶体结构和性能研究

合成了一种锌配位聚合物{[Zn(H2O)2(L)(phen)].3H2O}n(1),其中,H2L=1-氨基-8-萘酚-3,6-二磺酸并利用元素分析、红外、紫外、荧光、热重和X-射线单晶衍射分析进行了表征。标题配合物属正交晶系,Pnma空间群,a=1.698 90(12)nm,b=0.661 88(11)nm,c=2.480 40(14)nm,V=2.789 1(5)nm3,Z=4,Mr=634.92,Dc=1.512 g.cm-3,R=0.058 6,wR=0.121 4。标题配合物呈现一维链状结构,链内L2-和phen配体之间存在π-π堆积作用,链与链之间通过氢键扩展为二维超分子网络。     

3,5-二氨基苯甲酸构筑的Zn(Ⅱ)、Cd(Ⅱ)两种配合物的合成及晶体结构(英文)

利用3,5-二氨基苯甲酸配体合成了2种新的配合物[Cd(diaba)(phen)2]NO3·H2O(1)和[Zn(diaba)(2,2′-bipy)2](2)(H2diaba=3,5-diaminobenzoic acid;phen=1,10-phenanthroline,2,2′-bipy=2,2′-bipyridine),并对其进行了元素分析、红外光谱和X射线单晶衍射测定。配合物1属于正交晶系,空间群为Fddd,a=1.425 81(7)nm,b=2.564 62(13)nm,c=3.092 47(17)nm。配合物2属于单斜晶系,空间群为C2/c,a=1.273 62 nm,b=1.592 78 nm,c=1.519 35 nm,β=107.334°。配合物1和2都为单核晶体。配合物1的结构单元由1个CdII、1个3,5-二氨基苯甲酸和2个phen构成。配合物2的结构单元由1个ZnII、1个3,5-二氨基苯甲酸和2个2,2′-bipy构成。两种配合物再通过氢键或π-π堆积形成三维超分子网络。研究了配合物的热稳定性和荧光性质。     

Micellar effects on photoinduced redox reactions of Fe(bpy)2(CN)2

Excitation of solutions of Fe(bipy)₂(CN)₂ by a 266-nm laser pulse produces a hydrated electron and the oxidized complex, Fe(bipy)₂ (CN)₂⁺, in the primary photochemical step, in homogeneous aqueous solution as well as in aqueous solutions containing cetyltrimethylammonium bromide (CTAB) or sodium dodecyl sulfate (SDS) micelles. In all cases nascent hydrated electrons react with ground state Fe(bipy)₂(CN)₂ to form Fe(bipy)₂(CN)₂⁻, and comparison of the decay constants in the three media (H₂O: k = 2.8 × 10¹⁰ M⁻¹ s⁻¹; CTAB: k = 2.9 × 10¹⁰ M⁻¹ s⁻¹; SDS: k = 5.5 × 10⁹ M⁻¹ s⁻¹), shows that the reaction is essentially unaffected by CTAB micelles but is much slower in SDS solution. Similar micellar effects were found for the back reaction between e_aq⁻ and Fe(bpy)₂(CN)₂⁺. Rate constants for the scavenging of the photogenerated hydrated electrons by methyl viologen (MV²⁺) cations and NO₃⁻ anions were measured in the three systems, and the results indicate that for scavenging by MV²⁺ the rate constants are decreased in the micelle systems (k in H₂O, 8.4 × 10¹⁰; CTAB, 3.5 × 10¹⁰ and SDS, 1.58 × 10¹⁰ M⁻¹ s⁻¹), whereas for NO₃⁻ the CTAB micelle decreases while the SDS micelle enhances the scavenging compared to water solution (k in H₂O, 8.3 × 10⁹; CTAB, 7 × 10⁸; and SDS, 2.05 × 10¹⁰ M⁻¹ s⁻¹). For the comproportionation reaction between Fe(bipy)₂(CN)₂⁺ and Fe(bipy)₂(CN)₂⁻ both micelles reduce the rate (k in H₂O, 3.3 × 10¹⁰; CTAB, 2.3 × 10¹⁰; and SDS, 1.05 × 10¹⁰ M⁻¹s⁻¹), but while the reaction of Fe(bipy)₂(CN)₂⁺ with MV⁺ is increased in CTAB compared to water, it is slowed in SDS (k in H₂O, 2.4 × 10¹⁰; CTAB, 8.9 × 10¹⁰; and SDS, 1.8 × 10¹⁰ M⁻¹s⁻¹). All effects observed in these microheterogeneous systems can be uniformly interpreted in terms of Coulombic interactions between the actual reactants and the charged surface of the micelles.     

Ferromagnetic exchange coupling in phosphonato-bridged dinuclear copper(II) compound with monoethyl (pyridyn-2-ylmethyl)phosphonate ligand (2-mpmpe): Cu2(2-mpmpe)2(H2O)2(NO3)2

The interaction of diethyl (pyridyn-2-ylmethyl)phosphonate (2-pmpe) with Cu(NO₃)₂ · 6H₂O leads to a partial hydrolysis of the starting ligand and formation of the compound of the formula Cu₂(2-mpmpe)₂(H₂O)₂(NO₃)₂, where 2-mpmpe = monoethyl (pyridyn-2-ylmethyl)phosphonate. The crystal and molecular structure of a copper(II) compound was determined by single X-ray diffraction method. Its structure consists of five-coordinated in distorted square planar geometry (CuNO₄ chromophore) copper(II) ions doubly bridged by OPO from phosphonate. The Cu?Cu distance is 4.69 Å. The crystal packing is determined by the interdinuclear hydrogen bond system, which leads to a three-dimensional (3D) H-bonds network. The compound was characterized by infrared, ligand field, EPR spectroscopy, and magnetic studies. The magnetic properties of the title compound investigated over the 1.8–300 K, revealed the occurrence of a weak ferromagnetic coupling through phosphonate bridge (J = 1.86 cm⁻¹) and interdimer superexchange coupling through H-bond network (zJ′ = −0.17 cm⁻¹). Spectroscopic and magnetic properties are presented in the light of crystal structure.     

[Cu(TO)2(H2O)4](PA)2的合成和晶体结构

[Cu(TO)₂(H₂O)₄](PA)₂ was prepared by mixing the aqueous solution of 1,2,4-triazol-5-one(TO) and Cu(PA)₂. The molecular structure and crystal structure of the title complex was determined by X-ray single crystal diffraction method. The crystal is triclinic, space group with a=0.7321(1)nm,b=0.7474(2)nm,c=1.3649(3)nm;α=88.65(2)°,β=85.63(1)°,γ=63.35(1)°;V=0.6655(2)nm³,Z=1. The Cu²⁺ coordinated with two TO molecule through its 2-nitrogen atom and four water molecules and showed an octahedral configuration.     

Syntheses and X-ray crystallographic studies of {[Ni(en)2(pot)2]0.5CHCl3} and [Ni(en)2](3-pytol)2

Two novel Ni(II) complexes {[Ni(en)₂(pot)₂]0.5CHCl₃} (3) {pot = 5-phenyl-1,3,4-oxadiazole-2-thione} (1) and [Ni(en)₂](3-pytol)₂ (4) {3-pytol = 5-(3-pyridyl)-1,3,4-oxadiazole-2-thiol} (2) have been synthesized using en as coligand. The metal complexes have been characterized by physical and analytical techniques and also by single crystal X-ray studies. The complexes 3 and 4 crystallize in monoclinic system with space group P21/a and P121/c, respectively. The complex 3 has a slightly distorted octahedral geometry with trans (pot)⁻ ligands while 4 has a square planar geometry around the centrosymmetric Ni(II) center with ionically linked trans (3-pytol)⁻ ligands. The π?π (face to face) interaction plays an important role along with hydrogen bondings to form supramolecular architecture in both complexes.     

Preparation and structural characterization of [RuCl2(CO)2{Te(CH2SiMe3)2}2] and [RuCl2(CO){Te(CH2SiMe3)2}3]

The objective of the present work was to synthesize mononuclear ruthenium complex [RuCl₂(CO)₂{Te(CH₂SiMe₃)₂}₂] (1) by the reaction of Te(CH₂SiMe₃)₂ and [RuCl₂(CO)₃]₂. However, the stoichiometric reaction affords a mixture of 1 and [RuCl₂(CO){Te(CH₂SiMe₃)₂}₃] (2). The X-ray structures show the formation of the cis(Cl), cis(C), trans(Te) isomer of 1 and the cis(Cl), mer(Te) isomer of 2. The ¹²⁵Te NMR spectra of the complexes are reported. The complex distribution depends on the initial molar ratio of the reactants. With an excess of [RuCl₂(CO)₃]₂ only 1 is formed. In addition to the stoichiometric reaction, a mixture of 1 and 2 is observed even when using an excess of Te(CH₂SiMe₃)₂. Complex 1 is, however, always the main product. In these cases the ¹²⁵Te NMR spectra of the reaction solution also indicates the presence of unreacted ligand.     

Synthesis and Anti-inflammatory Action of （η-C5H5 ）2Ti（ Sal）2 and （η-C5H5 ）2Ti（Clo）2

IntroductionSince K pf[1]discovered that dicyclopenta die-nyltitanium dichloride possesses antitumour action in1979,a large number of cyclopentadienyltitanium com-plexes with different substituents have been synthe-sized[2,3].The experimental data reveal …     

配合物[Cd(NIT4Py)2][Au(CN)2]2的合成与晶体结构

A Cd(II)-nitronyl nitroxide radical complex with dicyanoaurate(I) bridges [Cd(NIT4Py)₂][Au(CN)₂]₂, was synthesized and characterized by elemental analyses, IR spectrum and X-ray diffraction single-crystal structure analysis. Crystal data for the complex: triclinic, space group P1, a=0.720 9(11) nm, b=0.960 3(15) nm, c=1.284(2) nm, α=75.38(2)°, β=85.46(2)°, γ=68.38(2)°, V=0.800(2) nm³, Z=1, and R₁ [I>2σ(I)]=0.055 8. The title complex consists of infinite one-dimensional chains of [Cd(NIT4Py)₂][Au(CN)₂]₂, in which [Cd(NIT4Py)₂] moieties are conne-cted by [Au(CN)₂]^- μ₂-bridging ligands. Each cadmium(II) ion is six-coordinated in a distorted and centrosymmetric octahedral environment. CCDC: 258357.     

混合纳米氢氧化镍的球镍电极材料的电化学活性研究

采用配位沉淀法制备出了Ni(OH)₂样品，经XRD测试为β-Ni(OH)₂，TEM测试结果表明其为平均粒径50nm左右的不规则的颗粒。将所制备的纳米Ni(OH)₂按8wt%的比例在球镍中混合后制成电极，可使正极的比容量提高11%左右。热分析表明，纳米Ni(OH)₂的电化学活性高于球镍的电化学活性。激光拉曼光谱的测试结果说明了8wt%混合后制成的纳米电极确实有较好的放电容量，同时也证实了用拉曼光谱可以表征电极材料的充放电     

Insulin-like model complexes: Synthesis,spectra characterization and crystal structure of two novel oxovanadium complexes with poly(pyrazolyl)borate ligands VO(HB(pz)3)(H2B(pz)2) and VO(B(pz)4)2

Two new oxovanadium (IV) complexes VO(HB(pz)₃)(H₂B(pz)₂) (1) and VO(B(pz)₄)₂ (2) have been obtained by the reaction of oxovanadium sulfate with the corresponding ligands KHB(pz)₃, KH₂B(pz)₂ and KB(pz)₄, respectively. The two complexes were characterized by elemental analyses, IR, UV–Vis and X-ray diffraction. Complex 1 crystallizes in the orthorhombic space group, Pca2₁. Complex 2 crystallizes in the orthorhombic space group, Pna2₁. In both complexes, five nitrogen atoms and one oxygen atom coordinate to the vanadium atom, forming a distorted octahedral geometry (VON₅). In addition, related spectra characterization, hydrogen-binding properties, structural configuration and quantum chemistry calculations are also discussed.     

Preparation, crystal structure and magnetic properties of Ni2(dpa)2(pyz)(H2O)4

A Ni(II)-based dimer structure, Ni₂(dpa)₂(pyz)(H₂O)₄ (dpa = 2,6-pyridine dicarboxylic acid dianion, pyz: pyrazine), has been prepared using hydrothermal synthesis and the solid-state magnetic properties have been evaluated. In the dimeric structure, the planar tridentate 2,6-pyridine dicarboxylic acid dianion coordinates to a Ni(II) ion in a meridional fashion and defines the equatorial plane of the complex. The fourth equatorial coordination site is then occupied by a pyrazine molecule that functions as a linear bidentate ligand bridging two Ni(II) complexes to form a dimer. The axial positions of each Ni(II) complex are occupied by two water molecules to form a distorted octahedral geometry. Susceptibility and magnetization measurements show that both intra-dimer and inter-dimer exchange interactions are weakly antiferromagnetic. The fitting of the magnetic data also indicates the existence of a large axial zero-field splitting term that contributes to the small magnetization even under high fields.