First transition metal coordination compound supported on metal–oxygen cluster with bicapped quasi-Keggin structure: [Cu(en)2(H2O)]4[Cu(en)2]3.5[PMoVI8VIV6O42Cu(en)(1,10′-phen)]3·14H2O

A novel compound, [Cu(en)₂(H₂O)]₄[Cu(en)₂]_3.5[PMo^VI₈V^IV₆O₄₂Cu(en)(1,10^′-phen)]₃·14H₂O 1 (en = ethylenediamine, phen = phenanthroline), was synthesized hydrothermally (170 °C, 10 days, autogeneous pressure) and characterized by IR, ESR, elemental analyses and X-ray crystallography. The results of structure determination show that compound 1 contains three different structure cluster anions [PMo^VI₈V^IV₆O₄₂]⁷⁻ supporting complex cation [Cu(en)(1,10^′-phen)]²⁺, in which one cluster anion possesses typical bicapped Keggin structure, while other two polyanions only have bicapped quasi-Keggin structures, and [Cu(en)(1,10^′-phen)]²⁺ is linked through oxygen atoms to different V positions of two bicapped quasi-Keggin units.     

Inorganic–organic hybrid material containing β-cage: {[H2(en)]Co2(ox)(V4O12)}n

By using an organic ligand, a new inorganic–organic hybrid compound of cobalt oxalate-vanadate, {[H₂(en)]Co₂(ox)(V₄O₁₂)}_n 1, where en = ethylenediamine, ox = oxalic acid, has been synthesized hydrothermally from V₂O₅,CoCl₂·6H₂O,H₂C₂O₄·2H₂O and en. Crystal data 1, orthorhombic, Cmcm space group, a=11.624(2), b=9.968(2), c=14.900(3) Å, R1=0.0298, wR2=0.1172. Compound 1 possesses a three-dimensional open-framework with β-cage and is an antiferromagnetic matter.     

Cu(DMe-H2biim)(OAc)2催化甲醇氧化羰基化合成碳酸二甲酯

以Cu(OAc)2为铜源,2,2'-联咪唑(H2biim)、1,1'-二亚甲基-2,2'-联咪唑(DMe-H2biim)和1,1'-邻二甲苯-2,2'-联咪唑(Oxy-H2biim)为配体,研究了其在甲醇氧化羰基化合成碳酸二甲酯(DMC)反应中的催化性能,并采用FTIR、TG和CO-TPR对Cu(DMe-H2biim)(OAc)2进行了表征。结果表明,DMe-H2biim中亚甲基的给电子效应使其比H2biim和Oxy-H2biim能更好地促进DMC的合成,且配合物Cu(DMe-H2biim)(OAc)2比等物质的量的Cu(OAc)2和DMe-H2biim混合物具有更高的催化活性。在Cu(DMe-H2biim)(OAc)2为催化剂,反应时间为4h,反应温度为110℃,催化剂浓度为0.014 mol/L的条件下,DMC的转化数(TON)为20.4,DMC选择性为95.8%。     

First two-dimensional framework material constructed from bicapped Keggin structure clusters: [Cu(en)2(H2O)]{[PMoVI8VIV6O42Cu(en)2][Cu0.5(en)]3} · 5.5H2O

The hydrothermal reaction of CuCl₂ · 2H₂O, Na₂MoO₄ · 2H₂O, NH₄VO₃, ethylenediamine (en) and H₃PO₄ yields a novel two-dimensional open-framework material. The extended structure consists of a network of {PMo₈V₆O₄₂ [Cu(en)₂]}⁵⁻ cages, with each cage connected to three other neighboring units via [Cu(en)₂]²⁺ bridging groups.     

Cu(2,2‘-bipy)(H2O)V2O6的合成及结构

以硝酸铜、2,2-联吡啶及Na3VO4用水热法在170℃合成出一种钒酸铜新化合物Cu(2,2'-bipy)(H2O)V2O6(1).化合物1的结构为一种一维链状化合物,其链状结构是以[Cu(2,2'-bipy)(H2O)]2 基团将[V4O12]4-环状的结构连接而成.     

A novel two-dimensional network self-assembled by the narrowest ladder cations [Cu(CH3COO)(bpe)(H2O)]nn+ containing the Cu2(μ-O)2 cores and the dimeric anions [Cu2(nta)2(bpe)]2− through hydrogen-bonding interaction

A novel complex [Cu(CH₃COO)(bpe)(H₂O)]_n·n/2[Cu₂(nta)₂(bpe)] ·6nH₂O) (bpe=trans-1,2-bis(4-pyridyl)ethylene) was synthesized and characterized. The molecule structure shows that it is composed of the ladder-like double chain cations [Cu(CH₃COO)(bpe)(H₂O)]_nⁿ⁺ and the dimeric anions [Cu₂(nta)₂(bpe)]²⁻. Through bridging oxygen atom of the acetate, the Cu₂ (μ-O)₂ core is formed. The ladder-like chain cation is the narrowest ladder [3.422(3) Å]. Two-dimensional undulating network is constructed by the cations and the dimeric anions through hydrogen-bonding interactions.     

[Y2(H2O)(BDC)3(DMF)]·(DMF)3: A rare 2-D (42.6)(45.6)2(48.62)(49.65.8) net with multi-helical-array and opened windows

In this work, we present a rare earth metal–organic framework, Y₂(H₂O)(BDC)₃(DMF)]·(DMF)₃ (BDC = 1,3-benzenedicarboxylate) 1, with a rare 2D (4².6)(4⁵.6)₂(4⁸.6²)(4⁹.6⁵.8) net, helical tubes with opposite chirality interweaving of triple-helical chains, opened windows and high thermal stability.     

Solvent/C60 exchange on Ir(CO)(PPH3)2(Cl)(η2-C60) and solvent/solvent’ exchange on Ir(CO)(PPH3)2(Cl)(solvent)

Dissociation of C₆₀ from Ir(CO)(PPh₃)₂(Cl)(η²-C₆₀) in a binary mixture of solvents (solvent₁ and solvent₂) produced non-equilibrium mixtures of Ir(CO)(PPh₃)₂(Cl)(solvent₁) and Ir(CO)(PPh₃)₂(Cl)(solvent₂). Once the solvated species were produced, they underwent a relative fast solvent exchange between them to produce an equilibrium mixture.     

The encapsulation of [Cu(en)2]2+ (en=ethylenediamine) by a novel three-dimensional CuII–MoIV bimetallic porous coordination polymer containing zigzag-ladder structure

The neutral three-dimensional cyano-bridged bimetallic coordination polymer, {[Cu(en)₂][Cu(en)][Mo(CN)₈]}_n·4nH₂O (en=ethylenediamine), has been synthesized and characterized. X-ray study shows that the asymmetric unit of the three-dimensional Cu(II)–Mo(IV) polymeric assembly consists of two half [Cu(en)₂]²⁺ cations, a [Cu(en)]²⁺ cation and a [Mo(CN)₈]⁴⁻ ion, together with four water molecules. The latter Cu site is coordinated by two N atoms from an en ligand and by three cyanides in a distorted square-pyramidal environment. The Cu(II) ions of the two [Cu(en)₂]²⁺ cations on the centers of inversion reside in an elongated octahedral geometry, and one of the [Cu(en)₂]²⁺ cations is encapsulated in a ‘box’ formed by two pairs of co-lateral Cu₂Mo₂(CN)₄ 12-membered macrocyclic units. The Mo(VI) atom is coordinated by eight cyanides in an irregular square antiprism. Five of these acting as bridging units connect the Mo and the three Cu atoms to form an infinite three-dimensional porous network containing a zigzag-ladder structure.     

聚丙烯聚乙烯共混研究(1)(2)

采用工业用注射机进行共混研究。得出在PP∶HDPE=75∶25时,共混物具有好的机械性能,并讨论了温度、转速对共混的影响。     

Synthesis,structure, and properties of two novel copper(II) complexes, [Cu(phen)(L)2]·6H2O and [Cu(phen)3]·(ClO4)2

Two novel copper(II) complexes, namely [Cu(phen)(L)₂]·6H₂O (1) and [Cu(phen)₃]·(ClO₄)₂ (2) have been synthesized under mild condition (HL = 5-methyl-1H-pyrazole-3-carboxylic acid, phen = 1,10-phenanthroline). We report the structural evidence of discrete water decamer conformation in the solid state. These units are found to act as supramolecular glue in the aggregation of mononuclear copper(II) complex to give a three-dimensional network through hydrogen-bonding. The preliminary investigation on the thermal behavior and the anion exchange property of the complexes are presented.     

Cu(Ⅱ)配合物[Cu(fiac)(1,10-phen)]·H_2O的合成、结构及性质研究

以5-氟水杨酸和邻菲罗啉为定向配体,与乙酸铜反应经溶剂热法合成了一个新的单核铜(Ⅱ)配合物[Cu(fiac)(1,10-phen)]·H2O(1)(Hfiac=5-氟水杨酸,1,10-phen=邻菲罗啉),并对结构进行了单晶X-射线衍射表征、元素分析和红外光谱分析。配合物1属于三斜晶系,Pī空间群,晶胞参数a=1.11401(6)nm,b=1.20947(10)nm,c=1.40478(17)nm;α=7.2680(11)°,β=75.090(9)°,γ=76.300(6)°,V=1719.6(3),Z=2,Dc=2.425g·cm-3,R1=0.0411,wR2=0.1108,S=1.110。配合物1中的Cu(Ⅱ)离子分别与来自二齿配体Hfiac上的两个O原子和来自邻菲罗啉配体上的两个N原子配位,形成平面构型。通过对配合物1的荧光性能研究,结果表明其具有一定的荧光特性。     

Synthesis,characterization and weak ferromagnetic coupling in [Cu2(μ3-CO3)(SCN)2(py)4]n

The crystal structure of a novel [Cu₂(μ₃-CO₃)(SCN)₂(py)₄]_n complex has been determined. It comprises of [CuCO₃Cu]_n infinite chains, running along the a-axis, and is in this aspect similar to the previously described [Cu(CO₃)(4-aminopyridine)₂]·H₂O complex. The FTIR spectrum of [Cu₂(μ₃-CO₃)(SCN)₂(py)₄]_n has been recorded and analyzed. A CuCO₃Cu intrachain coupling between Cu(II) atoms has been found to be responsible for the weak ferromagnetic properties of [Cu₂(μ₃-CO₃)(SCN)₂(py)₄]_n.     

配位聚合物[Cu(bipy)(H_2O)_2]SO_4的合成及晶体结构表征

在水醇溶液中合成了标题配位聚合物[Cu(bipy)(H2O)2]SO4(bipy=2,2-′bipyridine),进行了元素分析、X射线衍射等表征。X射线衍射结果表明,此配合物属单斜晶系,空间群为Cc,晶胞参数为:a=1.5138(2)nm,b=1.2455(8)nm,c=0.7001(8)nm,β=106.013(3)°,V=1.2690(0)nm3,Z=4,Dc=1.841 g/cm3,μ=1.913 mm-1,F(000)=716。配合物中的金属铜离子与一个2,2′-联吡啶、2个水分子配位,形成一个变形的四边形结构。配合物通过O-H…O氢键构建为三维超分子。     

溶剂极性对配合物Cu(L-trp)(Aa)稳定性的影响

应用pH电位滴定法研究了三元配合物Cu(L-trp)(Aa)[L-trp(色氨酸根),Aa-=L-leu(亮氨酸根),L-phe(苯丙氨酸根),L-tyr(酪氨酸根)]在水和j=0.20、0.40及0.60二氧六环-水混合溶剂中的稳定性[t=25℃,I=0.1mol/L NaClO4].三元配合物相对稳定性用δK{=△logK[=log KCu Cu (L-trp)(Aa)-log KCu Cu(L-trp)-log KCu Cu(Aa)]-△logK(S)[=1/2(△logK(L-op) △logK(Aa) log2)]}表示.结果表明:与L-丙氨酸(L-ala)配合物Cu(L-trp)(L-ala)相比,所有这些配合物均具有相对较高的8K值,表明配合物分子内存在着额外的稳定化作用.这种稳定性化作用可能主要归因于三元配合物分子内氨基酸侧链之间的疏水作用,并且随着氨基酸側链结构及溶剂极性变化而变化.     

Cu(NH3)2(FOX-7)2的晶体结构和热行为

用l,1-二氨基-2,2-二硝基乙烯的钾盐[K(FOX-7)·H2O]和硝酸铜在氨水体系中合成了Cu( NH3)2(FOX-7)2,并培养得到了单晶.该晶体为单斜晶系,空间群P21/c,a=0.68818(7)nm,b=O.73083 (8) nm,c=1.319 66(14)nm,β=95.986°,V=0.6600...     

Synthesis,structure and magnetic properties of a trinuclear cyano-bridged complex [Cu(bappz)(μ-NC)Ni(CN)2(μ-CN)Cu(bappz)](ClO4)2 {bappz=1,4-bis(3-aminopropyl)piperazine}

The bimetallic trinuclear complex [Cu(bappz)(μ-NC)Ni(CN)₂(μ-CN)Cu(bappz)](ClO₄)₂ (bappz=1,4-bis(3-aminopropyl)piperazine) has been prepared from the reaction of [Cu(bappz)](ClO₄)₂ and K₂[Ni(CN)₄] in water and its crystal and molecular structure has been determined. The structure consists of a trinuclear [Cu(bappz)(μ-NC)Ni(CN)₂(μ-CN)Cu(bappz)]²⁺ cation and two perchlorate anions. The bridging [Ni(CN)₄]²⁻ anion is coordinated by two [Cu(bappz)]²⁺ cations through two cyano groups, providing a novel trinuclear structure with the Cu–(NC)–Ni–(CN)–Cu linkage. The nickel(II) ion is four-coordinated by carbon atoms from four cyano groups (two of them, in trans position, form a bridge) in a square planar arrangement, whereas both the copper(II) ions are five-coordinated by four bappz nitrogens and one cyanide nitrogen in a distorted square–pyramidal geometry. The temperature dependence of magnetic susceptibility was measured for this compound over the range of 2–300 K. The magnetic investigation showed the presence of a very weak antiferromagnetic interaction (superexchange interaction parameter J=−0.54 cm⁻¹) between the copper atoms through the diamagnetic [Ni(CN)₄]²⁻ ion.     

Synthesis,structure and properties of a new copper (II) complex, [Cu2(4,4′-bpy)5(H2O)4](ClO4)4(4,4′-bpy)(DMF)2(H2O)2

A new copper (II) complex with formula [Cu₂(4,4′-bpy)₅(H₂O)₄](ClO₄)₄(4,4′-bpy)(DMF)₂(H₂O)₂ has been synthesized by reaction of 4,4′-bpyridine (4,4′-bpy) with Cu(ClO₄)₂. While strong hydrogen bonds play central roles in the formation of the 3D structure, the combined influence of the weak interactions such as C–H?O bonds, anion?π and C–H?π interactions are also evident in the structure. The preliminary investigation on the thermal property of the complex is presented.     

配合物[Cu(Phen)(H_2O)(p-CNC_6H_4COO)Cl]·H_2O的结构及性质研究

采用溶液法在室温水-乙醇溶液中,以CuCl2·2H2O、一水合邻菲啰啉(Phen·H2O)和对氰基苯甲酸(p-CNC6H4COOH,HCBA)为原料合成了标题配合物[Cu(Phen)(H2O)(CBA)Cl]·H2O。通过X-射线衍射法测定配合物的晶体结构,结构分析表明,中心Cu(Ⅱ)离子配位数为5,构成CuN2O2Cl四方锥配位模式。通过O—H…O氢键形成一维超分子带,超分子带又经带间C—H…O氢键作用形成超分子层,并经C—H…N氢键作用堆积组装形成三维超分子构造。并对其进行红外光谱、元素分析、粉末X-射线衍射、差热分析等表征。对配合物磁性做了进一步测试,在2~300 K区间遵循韦斯定理χm(T+0.10)=0.44 cm3·K·mol-1。并采用Van Vleck方程对配合物进行了拟合,最佳拟合结果为g=2.156(1),zJ'=-0.138(4),一致性因子为R=3.607×10-8。磁性测试结果表明Cu(Ⅱ)离子之间存在较弱的反铁磁耦合作用。