B3O4(OH) · 0.5(C4H10N2): First organic–inorganic hybrid borate with a neutral layered framework

A novel hybrid borate B₃O₄(OH) · 0.5(C₄H₁₀N₂) 1 was synthesized under milder hydrothermal conditions. The product was characterized by a combination of elemental analysis, FT-IR, thermogravimetric analysis and powder X-ray diffraction, as well as single-crystal X-ray diffraction studies. The structure consists of two types of inorganic borate helices cohered by piperazine rings, giving rise to a neutral hybrid sheet. The adjacent layers are stacked in a parallel fashion and further stabilized by hydrogen bonding interactions.     

Hydrothermal synthesis,crystal structure and photoluminescent property of a novel 3-D [La2(C2O4)2(NO3)(OH)(H2O)] · 3H2O

A novel 3D [La₂(C₂O₄)₂(NO₃) (OH)(H₂O)] · 3H₂O 1 has been synthesized under hydrothermal conditions and characterized by elemental analyses, IR, TGA, X-ray powder diffraction, X-ray single crystal diffraction and photoluminescence. The bridging modes of both nitrates and oxalates in compound 1 are uncommon. We have unexpectedly generated an unusual compound by using the simplest ligands, oxalates and nitrates in the presence of nicotinate (HIN).     

三维超分子化合物[Zn(C6H4O2N)2·(H2O)4]n的水热合成及晶体结构

用2-羧基吡啶和六水合氯化锌反应制备了一种新的三维氢键超分子配合物,经X-射线衍射分析确定了单晶结构。该晶体属单斜晶系,P2(1)/n空间群,晶胞参数为:a=9.836(2),b=5.2256(10),c=14.611(3),Mr=381.64,β=90.01(3)°,V=751.0(3)3,Z=2,Dc=1.688Mg.m-3,F(000)=392,μ=1.680mm-1,R=0.0258,wR=0.0612。共收集2159个衍射数据,其中1273个为独立衍射点(Rint=0.0332),可观测点数1139个(I>2σ(I))。结果表明,在组成该超分子体系的基本结构单元[Zn(C6H4O2N)2.(H2O)4]中,Zn(Ⅱ)离子形成六配位的畸变的八面体构型,配合物单元之间通过氢键OH…O相互连接,形成了无限延伸的具有网状结构的三维超分子体系。     

三维超分子化合物[Zn(C6H4O2N)2·(H2O)4]n的水热合成及晶体结构

用2-羧基吡啶和六水合氯化锌反应制备了一种新的三维氢键超分子配合物,经X-射线衍射分析确定了单晶结构.该晶体属单斜晶系,P2(1)/n空间群,晶胞参数为a=9.836(2)(A),b=5.2256(10)(A),c=14.611(3)(A),Mr=381.64,β=90.01(3)°,V=751.0(3)(A)3,Z=2,Dc=1.688Mg·m-3,F(000)=392,μ=1.680mm-1,R=0.0258,wR=0.0612.共收集2159个衍射数据,其中1273个为独立衍射点(Rint=0.0332),可观测点数1139个(I＞2σ(I)).结果表明,在组成该超分子体系的基本结构单元[Zn(C6H4O2N)2·(H2O)4]中,Zn(Ⅱ)离子形成六配位的畸变的八面体构型,配合物单元之间通过氢键OH…O相互连接,形成了无限延伸的具有网状结构的三维超分子体系.     

Interaction of [Rh(2)(O(2)CCH(3))(4)(H(2)O)(2)] and [Rh(2)(O(2)CCH(OH)Ph)(2)(phen)(2)(H(2)O)(2)](O(2)C-CH(OH)Ph)(2) With Sulfhydryl Compounds and Ceruloplasmin

The interaction of binuclear rhodium(II) complexes [Rh(2)(OOCCH(3))(4)(H(2)O)(2)], [Rh(2){OOCCH(OH)Ph}(2)(phen)(2)(H(2)O)(2)] {OOCCH(OH)Ph}(2), [Rh(2)(OOCCH(3))(2)(bpy)(2)(H(2)O)(2)](OOCCH(3))(2) and [Rh(2)Cl(2)(OOCMe)(2)(bpy)(2)](3H(2)O) with ceruloplasmin, cysteine, glutathione and coenzyme A have been investigated using. UV-Vis and CD spectroscopies. The complexes containing phen or bpy at pH = 7.4 and 4.0 are readily reduced with sulfhydryl compounds, while rhodium(II) acetate is relatively stable in these conditions. Complex [Rh(2){OOCCH(OH)Ph}(2)(phen)(2)(H(2)O)(2)] strongly changes structure of ceruloplasmin leading to the decrease of of alpha-helix content and loss of oxidase activity.     

配合物Pd(C4H2O4)(C4H8N2)0.5的合成及对苯酚的氧化羰基化的催化活性

A novel complex Pd(C4H2O4)(C4H8N2)0.5 has been synthesized by solvent thermal synthesis and used as a heterogeneous catalyst for direct synthesis of diphenyl carbonate (DPC) by oxidative carbonylation of phenol. In the reaction system of Pd(C4H2O4)(C4H8N2)0.5/Cu(OAc)2/ tetrabutylammonium bromide/ hydroquinone/ 4A molecular sieves, the effect of reaction temperature, time and CO pressure on catalytic activity were investigated, and the results revealed that the catalyst could catalyze oxidative carbonylation of phenol effectively. Under suitable reaction conditions of T=90℃, t=4h, p(O2)=0.3 MPa, p(CO)=3.9 MPa and CH2Cl2 as solvent, the turnover number (TON) of diphenyl carbonate can reach about 13.50 (mol-DPC/mol-Pd), which is higher than the TON for pure PdCl2 under the same reaction conditions.     

[Zn(H2O)4][B6O10]: An open-framework borate with acentric structure

An open-framework borate [Zn(H₂O)₄][B₆O₁₀] with acentric structure, has been successfully obtained for the first time under solvothermal conditions. It has been characterized by powder and single crystal X-ray diffraction, IR spectroscopy, diffuse-reflectance spectroscopy and thermogravimetric (TG) analyses, respectively. It crystallizes in the orthorhombic system, space group Pna2₁, a = 11.3140(6) Å, b = 11.8995(7) Å, c = 8.6140(5) Å and Z = 4. In the structure, the alternative connections between [B₃O₇] units give rise to an unprecedented 3D borate framework with 11- and 10-MR channels, in which the [Zn(H₂O)₄]²⁺ complexes are located. It has a cut-off edge below 200 nm and exhibits second harmonic generation (SHG) efficiency approximately 0.4 times that of KH₂PO₄ (KDP).     

(H2en)0.5[BiO(OH)2(H2O)]: The first organic templated layered bismuthate

A novel 2-D organic templated bismuth–oxygen compound (H₂en)_0.5[BiO(OH)₂(H₂O)] (1) (en = ethylenediamine) has been synthesized in the presence of ethylenediamine acting as a template under mild hydrothermal conditions. The structure was determined by single crystal X-ray diffraction and further characterized by IR spectrum, elemental analysis, scanning electron microscopy (SEM), photoluminescence and thermogravimetric analysis. In the compound, the Bi atom was coordinated by eight oxygen atoms. The BiO₈ polyhedra share edges or corners with their neighbors to result in an anionic inorganic layer with protonated ethylenediamine cations occupied between layers. At ambient temperature, 1 shows a blue emission band which may be assigned to the ¹P₁–¹S₀ transitions of the s² electron of the Bi^3 + ion. To our knowledge, 1 is the first example of layered bismuthate templated by an organic amine.     

[CoI2(C6H4N3CH2CO2C4H2SCO2CH2C6H4N3)], a coordination polymer containing the thiophene-2,5-di(carboxylatomethylenebenzotriazole) bridging ligand: synthesis,structure, redox properties

The title complex was obtained by reacting CoI₂ with thiophene-2,5-di(carboxylatomethylenebenzotriazole) in dichloromethane. The single-crystal X-ray structure analysis of the green material reveals a polymeric chain of CoI₂ units, tetrahedrally coordinated and connected by the 3-nitrogen atoms of the two benzotriazole groups of the multifunctional ligand. The paramagnetic cobalt(II) polymer can be oxidised by hexachloroethane to give the corresponding cationic cobalt(III) complex [CoI₂(C₆H₄N₃CH₂CO₂C₄H₂SCO₂CH₂C₆H₄N₃)(H₂O)₂]⁺ which is diamagnetic and precipitates as the green–yellow chloride salt.     

无机-有机杂化硼酸盐晶体[C_6N_4H_20]_(0.5)[B_5O_6(OH)_4]的合成与表征

介绍了在低温水浴中采用溶剂蒸发法合成硼酸盐晶体[C6N4H20]0.5[B5O6(OH)4]的实验。分别采用X射线粉末衍射仪、热重分析仪和红外分析仪对样品进行了表征,通过对不同大型仪器的使用,能够使学生掌握仪器操作的方法、提高谱图解析的能力。该实验为最新的科学研究成果,知识点新颖,同时将无机合成实验与大型仪器表征有机的结合在一起,不仅能够提高学生的科研能力,还能培养学生的创新思维。     

(C_4H_(10)N_2H)_3HSiMo_(12)O_(40)纳米颗粒的摩擦学研究

在醇-水体系中,以H4S iMo12O40和哌嗪为原料制备了组成为(C4H10N2H)3HS iMo12O40的纳米颗粒,以透射电子显微镜(TEM)、扫描电子显微镜(SEM)、X射线粉末衍射仪(XRD)、傅立叶变换红外光谱仪(FT-IR)、紫外可见分光光度计(UV)、热分析仪(TG-DTA)等测试手段,对纳米颗粒的形貌、组成和结构进行了表征,并在机械式四球长时抗磨损试验机上考察了其摩擦学性能。分散型实验结果表明,化合物在有机溶剂中良好分散(除乙醚外),红外/紫外光谱和X射线粉末衍射表明,所合成的纳米颗粒具有杂多酸Keggin骨架结构无机核,透射电镜分析表明,颗粒平均粒径约为10 nm,热分析显示分解温度范围为200~425℃,作为新型有机/无机复合纳米润滑油添加剂,最佳添加浓度为0.35%时,在测试条件为负荷294 N,时间30 m in,转速1450 r/m in条件下,使磨斑直径减小22.7%,摩擦系数减小14%。     

Solvothermal synthesis,crystal structure and photoluminescent property of a novel 3-D magnesium metal–organic framework Mg1.5(μ5-btec)(H2O)2] · [H2N(CH3)2] · H2O

A novel 3-D magnesium metal–organic framework [Mg_1.5(μ5-btec) (H₂O)₂] · [H₂N(CH₃) ₂] · H₂O (btec = 1,2,4,5-benzenetetracarboxylic acid) has been synthesized under solvothermal conditions, and characterized by single-crystal X-ray structure determination, thermogravimetric analysis, X-ray powder diffraction, IR, and photoluminescent studies.     

Photochemical synthesis,structure and spectroscopic properties of [W(CO)4(C5H10N)2CH2]

Dipiperidylmethane (CH₂dipip) coordinates to photochemically created W(CO)₄ species to give a tungsten(0) complex [W(CO)₄(CH₂dipip)]. The structure of the new bidentate amine complex of tungsten(0) was established by spectroscopic methods (NMR, IR, UVVis) in solution and by single-crystal X-ray diffraction studies. A preliminary experiment indicates that the tungsten complex emits light at λ_max. 556 nm, when it is excited by λ_max. 523 nm in the solid state at room temperature.     

二维层状磷酸铝化合物[Al(HPO4)(H2PO4)(C10H8N2)]的合成与表征

利用溶剂热法成功地合成出一个二维层状磷酸铝化合物[Al(HPO4)(H2PO4)(C10H8N2)].通过X-ray粉末衍射、单晶X射线、ICP、元素分析及热重分析等对该化合物进行了表征.该化合物属于单斜晶系,空间群P21/c(No.14),晶胞参数a = 10.932(2) ?,b = 15.7183(3) ?, c = 8.4177(17) ?,α = 90o,β = 108. 95(3)o ,γ = 90o, V=1368.0(5)?3,Z=4.其骨架由AlO4N2八面体通过共顶点与H2PO4和HPO4四面体连接而形成(4,12)网络层状结构.该网层结构按AA方式堆积,同时相邻层的2,2'-联吡啶分子之间具有Pi-Pi键相互作用.该工作进一步丰富了磷酸铝化合物的结构化学,并且为实现定向设计和合成提供了实验和理论依据.     

Structural characterization of a layered double salt Mn3(OH)2(SO4)2(H2O)2 · K2SO4

The title layered double salt Mn₃(OH)₂(SO₄)₂(H₂O)₂ · K₂SO₄ (1) was obtained from a simple hydrothermal reaction of CdSO₄ · 8/3H₂O, MnCl₂ · 4H₂O, α-aminopyridine (apy) and KI. X-ray analysis reveals that the two-dimensional (2-D) sheet of 1 is built up of the dimers of edge-sharing Mn(1) octahedral, extended by the apices of Mn(2) octahedral together with μ₃ and μ₄ SO₄ groups. With free K⁺ ion as guest species, the 2-D sheets are further self-assembled into a 3-D supramolecular network with 1-D channels through the Ow-H ⋯ O hydrogen-bonded interactions. The magnetic property of 1 was investigated, and a classical behavior is observed with an antiferromagnetic order below 12.5 K.     

Syntheses and Characterization of Diorganotin Derivatives of 2-Mercapto-5-methyl-1,3,4-thiadiazole: X-ray Crystal Structure of Polymeric (C3H3S2N2) [(n-C4H9)6Sn3O(OH)2](C3H3S2N2)

Diorganotin derivatives of 2-mercapto-5-methyl-1,3,4 -thiadiazole, (R = Me 1, n-Bu 2, Ph 3, PhCH₂ 4), have been synthesized and characterized by IR, ¹H, ¹³C and ¹¹⁹Sn NMR spectroscopy. Among them, polymer 2 was also characterized by X-ray crystallography diffraction analysis. This revealed that 2 showed a unique tricyclic structure consisting of a fused five-membered Sn₂ON₂ ring and a four-membered Sn₂O₂ ring. These formed a planar N₂Sn₃O₂ skeleton, with distorted trigonal bipyramidal coordination at the two tin centers and a distorted octahedral coordination at the other tin center. The supramolecular structure of polymer 2 was a 1D zig-zag polymeric chain stabilized by intermolecular O–H...S hydrogen bonds. An erratum to this article can be found at