新型磷-钒-氧层状化合物[H2en]2[H3O]6[Co(H2O)2(VO)8(OH)4(PO4)8]的水热合成与晶体结构

金属磷酸盐材料在吸附、离子交换、离子传导和催化剂方面有潜在的应用前景[1～5]. 近年来, 通过水热反应合成了一些A-V-P-O化合物. 在这些化合物中, A一般为碱金属或有机阳离子, 如层状结构的[H2N(C4H8)2NH2][(VO)4(OH)4(PO4)2][6] 和[H2N(C2H4)3NH2][(VO)8(HPO4)3(PO4)4*(OH)2]*2H2O[6], 一维链状结构的 [H2NCH2CH2NH3(VO)(PO4)][7], 手性双螺旋结构的 [(CH3)2NH2]K4[(VO)10(H2O)2(OH)4(PO4)7]*H2O[8]以及具有三维骨架结构的化合物 [H3N(CH2)3NH3K(VO)3(PO4)3][9], [H3N(CH2)3NH3]2[V(H2O)2(VO)6(OH)2(HPO4)3(PO4)5]*3H2O[10]和[H3N(CH2)2NH3][(VO)3(H2O)2(PO4)2(HPO4)4][11].     

Transfer Gibbs Energies of[Cr(Salen)(H2O)2]BPh4 From Water to Straight-chain Alkanol

Chromium(Ⅲ) is one essential nutrient that has been implicated as glucose tolerant factor(GTF) in the maintenance of normal carbohydrate and lipid metabolism. Schiff base complexes of chromium (Ⅲ) such as N,N' -ethylenebis (Salicylideneiminato) diaquochromium (Ⅲ) chloride[Cr(Salen)(H₂O)₂]Cl as a new kind of GTP model was shown to reduce the symptoms of diabetes significantly, hyperglycemia and cholesterol in diabetic rates^[l]. After studied the decomposition and characterization of[Cr(Salen)(H₂O)₂]Cl^[2], a new confound of[Cr(Salen)(H₂O)₂]BPh₄ is prepared and its transfer Gibbs energies(Δ_tr Go) from water to strait-chain Alkanols is studied in order to understand the thermodynamic properties of[Cr(Salen)(H₂O)₂]⁺ in different solvents.     

Hydrothermal Synthesis,Structure and Properties of a New Phosphomolybdate Based on Novel [Co(H2O)4(HP2Mo5O23)]8- Anions and [H8(H2O)16]8+ Water Cluster Cations

A pure inorganic [P₂Mo₅O₂₃]^6- based cobalt complex [H₈(H₂O)₁₆][Co(H₂O)₄(HP₂Mo₅O₂₃)₂] with a sandglass-like shape was synthesized and characterized by means of single-crystal X-ray diffraction, powder X-ray diffraction(PXRD), infrared spectroscopy(IR), thermogravimetry/differential scanning calorimetry(TG/DSC), ultraviolet-visible spectroscopy(UV-Vis) and cyclic voltammogram(CV). Single-crystal X-ray diffraction analysis reveals that the asymmetric unit of compound 1 consists of a half cobalt ion, one [P₂Mo₅O₂₃]^6- anion, two coordinated water molecules and eight lattice water molecules. It is especially intriguing to note that two [P₂Mo₅O₂₃]^6- clusters are symmetrical about the Co ion, like a sandglass. And a chair-like water cluster with an unprecedented centrosymmetric [H₈(H₂O)₁₆]⁸⁺ can be observed in compound 1. Additionally, the electrochemical and catalytic properties of compound 1 were also investigated.     

新的四帽Keggin结构的金属-氧簇合物[NiMo12O40H10{Ni(H2O)3}4]的水热合成与结构表征

多金属氧酸盐 (也称金属 -氧簇 )由于在催化、材料及医药等领域的应用日益广泛而备受关注 .近年来 ,一些新颖的非经典结构的化合物不断被合成出来 .如带二帽的 Keggin结构化合物 [V15O4 2 ]9- [1] ,[PV14 O4 2 ]9- [2 ] ,[As V14 O4 2 ]9- [3 ] ,[{ Mo8V7O4 2 } 2 ]14 - [4 ] ,     

Self-assembly of an Unprecedented Cynao-bridged One-dimensional 4f-3d Complex[Eu(DMF)4(H2O)2Cr(CN)6] H2O

Recently, there has been considerable interest in cyano-bridged lanthanide(Ⅲ) hexacyanometalate(Ⅲ) complexes LnM(CN)₆·nH₂O (M=Fe, Cr and Co) because of their potential as catalytic, semiconductive, and magnetic materials.^[1-8] In this study, we employed N,N-dimethylformamide (DMF) as a hybrid ligand to construct a bimetallic complex[Eu(DMF)₄(H₂O)₂Cr(CN)₆]·H₂O. It was synthesized as yellow crystals by the self-assembly of anhydrous EuCl₃ and (Bu₄N)₃[Cr(CN)₆] in MeOH and DMF. Single-crystal X-ray diffraction analysis shows that it consists of a cyano-bridged chain structure. The Eu atom is eight-coordinate with a distorted bicapped square antiprism geometry. Six oxygen atoms of two water molecules and four DMF molecules and two nitrogen atoms of the bridging CN ligands are bound to Eu with the Eu-O distance ranging from 2.368(7) to 2.447(8) Å. The bridging cyanides coordinate to the Europium(Ⅲ) ion[N(l)-Eu=2.543(9) Å and N(3)-EuA=2.543(8) Å] in a bent fashion with the bond angles of 164.0(9) for C(1)-N(1)-Nd and 155.1(7)。for C(3)-N(3)-EuA (A denotes the symmetry transformation:-x+l,y-l/2,-z+3/2). Each Cr(CN)₆ coordinates to two Eu(Ⅲ) ions using two cis cyanide ligands, while each Eu(DMF)₄(H₂O)₂ group connects two Cr(CN)₆ moieties in a cis fashion, giving rise to an unprecedented chain structure. Crystal data:monoclinic, space group P2₁/c, a=13.151(2), b=12.905(2), c=19.186(2) Å, β=109.70(1)°, V=3065.5(7) ų,Z=4, ρ_obs=1.531 Mg m^-3, S=1.024,R1=0.0540, R_w=0.1616.     

二维钨-钒簇聚物[Cu(en)2]2·[VⅤO44{Cu(en)2(H2O)}2]·3H2O的合成与表征

采用水热法合成了一个钨-钒簇聚物[Cu(en)₂]₂[V^Ⅴ{Cu(en)₂(H₂O)}₂]·3H₂O(1, en=乙二胺), 并通过X射线单晶衍射、 元素分析、 傅里叶变换红外光谱、 X射线粉末衍射、 热重分析、 价键计算、 X射线光电子能谱、 电子顺磁共振和磁性分析对其结构和性能进行了表征. 结果表明, 化合物1是以双支撑的四帽Keggin结构 [(V^ⅤO₄){Cu(en)₂(H₂O)}₂]^4- 钨-钒簇合物阴离子为基本结构单元, 与4个[Cu(en)₂]²⁺配合物阳离子以共价键和弱键相连接形成二维层状结构, 相邻层又通过氢键连接成三维超分子网络. 研究了化合物1的磁性及光催化降解罗丹明B的活性.     

Novel One-dimensional Cyano-bridged Chain Molecular-based Magnet[Ln(DMF)4(H2O)2Mn(CN)6·H2O]n:Crystal Structure,Long-range Magnetic Ordering,High Tc and Strong Coercive Behavior

There has been great interest in the study of the magnetic properties of molecular-based compounds^[1,2]. In the present work, we employed N,N-dimethylformide (DMF) as a hybrid ligand to synthesize a new family of cyano-bridged complexes contain rare earth and Manganese:[Ln(DMF)₄(H₂O)₂Mn(CN)₆·H₂O]_n (abbreviated as LnMn, Ln=Sm, Eu, Gd, Tb, Dy, Er) and the crystal data of former three complexes has been obtained, which display a remarkable variety of magnetochemical behavior and a rich structural chemistry.     

Structural diversity of lanthanide–amino acid complexes under near physiological pH conditions and their recognition of single-stranded DNA

We reported here four structures of lanthanide–amino acid complexes obtained under near physiological pH conditions and their individual formula can be described as [Tb₂(dl-Cys)₄(H₂O)₈]Cl₂ (1), [Eu₄(μ₃-OH)₄(l-Asp)₂(l-HAsp)₃(H₂O)₇] Cl · 11.5H₂O (2), [Eu₈(l-HVal)₁₆(H₂O)₃₂]Cl₂₄ · 12.5H₂O (3), and [Tb₂(dl-HVal)₄(H₂O)₈]Cl₆ · 2H₂O (4). These complexes showed diverse structures and have shown potential application in DNA detection. We studied the interactions of the complexes with five single-stranded DNA and found different fluorescence enhancement, binding affinity and binding stoichiometry when the complexes are bound to DNA.     

One-dimensional infinite chain crown ether complex:Synthesis and crystal structure of[Na(18C6)]2[Cu(mnt)2]·H2O

One-dimensional coordination polymers have attracted considerable interest in recent years because of the prospect of electrical, optical and magnetic properties. Crown ether can form one-dimensional infinite chain structure with transition metal complex. We synthesized the complexes of 18-crown-6 with Na₂[m{S₂C₂(CN)₂}₂](m=Cu, Ni, Pd, Pt; S₂C₂(CN)₂^2- mnt) and now report the structure of complex[Na(18C6)]₂[Cu(mnt)₂]·H₂O.     

Preparation and Characterization of Heteropoly-complex K_11[La(GaW_11O_39H_2)_2]· xH_2O

Heteropoly complexes K11[Ln(CaW 11O39H2)21 · x H2O(Ln=La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy ) have been prepared and analysed. Some properties such as thermal behavior, IK and UV spectra, X-ray powder diffraction, magnetic susceptibility and X-ray photoelectron spectrum have been investigated.     

Synthesis,Structure Characteristic and Thermal Behavior of Two New Metal-organic Azo-triazole Compounds: [Zn(phen)3]·ZTO·6H2O and[Cu(phen)3]·ZTO·6H2O

[Zn(phen)₃]·ZTO·6H₂O(1) and[Cu(phen)₃]·ZTO·6H₂O(2) were synthesized by the reaction of Zn(NO₃)₂·6H₂O/Cu(NO₃)₂·3H₂O with 4,4-azo-1H-1,2,4-triazol-5-one(ZTO) and 1,10-phenanthroline(phen). The two compounds were characterized by elemental analysis and IR spectrum analysis, respectively. Compound 1 was also characterized by single crystal X-ray diffraction analysis. For compound 1, the coordination geometry around the Zn²⁺ is a distorted octahedron, with the bite angles of 76.7(3)°-77.6(4)° for all three phen ligands. Moreover, the thermal behaviors and thermal decomposition kinetics were studied and analyzed. Besides, thermal stability and safety parameters(T_SADT, T_b) are 164.7 and 166.4℃ for compound 1, and 149.6 and 150.8℃ for compound 2, respectively.     

Synthesis,Structure and Characterization of Three Metal Molybdate Hydrates: Fe(H2O)2(MoO4)2·H3O,NaCo2(MoO4)2(H3O2)and Mn2(MoO4)3·2H3O

Three metal molybdate hydrates,Fe(H2O)2(MoO4)2·H3O(FeMo),NaCo2(MoO4)2(H3O2)(CoMo)and Mn2(MoO4)3·2H3O(MnMo),were synthesized by the mixed-solvent-thermal methods and characterized by singlecrystal X-ray...     

Synthesis and X-ray crystal structures of bis(bis(μ2-2-aminoethanolato–N,O,O)–cobalt(III))–cobalt(II) hydrate, tris(biscyclohexylammonium)μ-hydroxo–bis(μ2-nitro–N,O)–hexanitro–dicobaltate(III) and biscyclohexylammonium nitrate(III)

Two new cobalt complexes: Co₃(NO₂)₄(NH₂CH₂CH₂O)₄·H₂O (1) and (NH₂(C₆H₁₁)₂)₃[Co₂(NO₂)₈OH]·3H₂O (2) and the compound (NH₂(C₆H₁₁)₂)NO₂ (3) were synthesised and their structures have been determined using single-crystal X-ray diffraction. Compound 1 consists of two centrosymmetrical trinuclear complexes and a water molecule of crystallization. Ligands coordinated to Co atoms are nitro and aminoethanolato groups. Structure 2 is built up of biscyclohexylammonium cations, dinuclear anions with hydroxo and nitro groups coordinated to Co atoms and water molecules. The coordination of Co atoms in both structures is roughly octahedral.     

Low-temperature heat capacity and thermodynamic properties of crystalline [Re2(Ala)4(H2O)8](ClO4)6 (Re = Eu, Er; Ala = alanine)

[Re₂(Ala)₄(H₂O)₈](ClO₄)₆ (Re=Eu, Er; Ala=alanine) were synthesized, and the low-temperature heat capacities of the two complexes were measured with a high-precision adiabatic calorimeter over the temperature range from 80 to 370 K. For [Eu₂(Ala)₄(H₂O)₈](ClO₄)₆, two solid–solid phase transitions were found, one in the temperature range from 234.403 to 249.960 K, with peak temperature 243.050 K, the other in the range from 249.960 to 278.881 K, with peak temperature 270.155 K. For [Er₂(Ala)₄(H₂O)₈](ClO₄)₆, one solid–solid phase transition was observed in the range from 270.696 to 282.156 K, with peak temperature 278.970 K. The molar enthalpy increments, ΔH_m, and entropy increments,ΔS_m, of these phase transitions, were determined to be 455.6 J mol⁻¹, 1.87 J K⁻¹ mol⁻¹ at 243.050 K; 2277 J mol⁻¹, 8.43 J K⁻¹ mol⁻¹ at 270.155 K for [Eu₂(Ala)₄(H₂O)₈](ClO₄)₆; and 4442 J mol⁻¹, 15.92 J K⁻¹ mol⁻¹ at 278.970 K for [Er₂(Ala)₄(H₂O)₈](ClO₄)₆. Thermal decompositions of the two complexes were investigated by use of the thermogravimetric (TG) analysis. A possible mechanism for the thermal decomposition is suggested.     

Non-isothermal Decomposition Kinetics of [Cu（en）2H2O] （FOX-7）2·H2O

The thermal behavior and non-isothermal decomposition kinetics of [Cu（en）2H2O]（FOX-7）2·H2O （en=ethylenediamine） were studied with DSC and TG-DTG methods.The kinetic equation of the exothermal process is dα/dt=（10^17.92/β）4α^3/4exp（-1.688×10^5/RT）.The self-accelerating decomposition temperature and critical temperature of the thermal explosion are 163.3 and 174.8 ℃,respectively.The specific heat capacity of [Cu（en）2H2O]（FOX-7）2·H2O was determined with a micro-DSC method,with a molar heat capacity of 661.6 J·mol^-1·K^-1 at 25 ℃.Adiabatic time-to-explosion was also estimated as 23.2 s.[Cu（en）2H2O]（FOX-7）2·H2O is less sensitive.     

稀土冠醚类配合物的研究(Ⅺ)——硝酸钪、钇与二苯并-24-冠-8的固态配合物的合成及性质

以无水乙腈为反应介质,合成了硝酸钪及硝酸钇与DB24C8的固态配合物,确定其组成为Sc(NO₃)₃·DB24C8·2H₂O和[Y(NO₃)₃]₄·(DB24C8)₃·8H₂O,并对冠醚及其配合物的某些性质进行了对比研究。     

A Novel Dimer--Heteropolytungstate with a Vanadium Atom as the Centre--Synthesis and Structural Characterization of (H3O)4[VW12O40Na(H2O)4]2

A novel dimer-tungstovanadate,(H3O)4［VW12O40Na(H2O)4］2,was hydrothermally synthesized and structurally characterized by single crystal X-ray diffraction,IR spectra,TGA-DSC thermal analysis and polarograpy.The yellowish crystal crystallized in the triclinic system,space group ,a=1.464 5(3) nm,b=1.4686(3) nm,c=1.4111(3) nm,α=111.82(2)°,βA novel dimer-tungstovanadate,(H3O)4［VW12O40Na(H2O)4］2,was hydrothermally synthesized and structurally characterized by single crystal X-ray diffraction,IR spectra,TGA-DSC thermal analysis and polarograpy.The yellowish crystal crystallized in the triclinic system,space group ,a=1.464 5(3) nm,b=1.4686(3) nm,c=1.4111(3) nm,α=111.82(2)°,β=93.17(3)°,γ=117.47(3)°,V=2.2106(8) nm3,Z=1,Dc=4.552 g.cm-3,λ(Mo Kα)=0.071073 nm,μ=31.402 mm-1,F(000)=2648,R=0.0780.The title compound consists of two Keggin structure units linked together with two hydrated sodium cations to form a dimer with a porous structure with the pore dimension of 0.766 nm×0.7785 nm.     

新型层状氟化磷酸铝[C4H12N2][Al2(PO4)2(H2O)2F2]的水热合成与表征

自从1982年Wilson等发现一类新型微孔材料磷酸铝分子筛(AlPO4-n)以来,大量具有新颖结构的磷酸铝化合物被合成出来,它们在催化、离子交换、吸附和主-客体组装等方面均具有潜在的应用前景,这类化合物大多是在水热或溶剂热体系中和有机模板剂存在条件下合成的,1978年,Flanigen等首先在反应体系中加入氟离子作矿化剂合成了硅晶体,后来,氟离子方法在硅铝体系和金属磷酸盐体系中也得到了广泛的应用,氟离子在反应过程中起到矿化剂或结构导向剂的作用,     

Hydrothermal synthesis, crystal structures and luminescent properties of two new Ln(III)–succinate (Ln=Eu, Tb) complexes exhibiting three dimensional networks

Two new coordination polymers, [Eu₂(L)₃(H₂O)₂]_n 1 and {[Tb₂(L)₃(H₂O)₂]·H₂O}_n 2, (H₂L=succinic acid) have been synthesized by the reaction of H₂L with nitrate salts of Eu(III) or Tb(III) under hydrothermal conditions. The X-ray diffraction analysis reveals that the two complexes are constructed by L bridging the chains of edge-sharing EuO₈(H₂O) or TbO₈(H₂O) polyhedra to form 3D network structure. 1 and 2 possess different topological structures due to the difference in the conformations of L. The solid photoluminescence of 1 and 2 was also investigated in room temperature.     

二苯羧酸类稀土配合物对藤黄微球菌抑制作用的微量热研究

合成了4例二苯羧酸类稀土配合物:[Re_2(oba)_3(H_2O)_5]·H_2O[Re=La(1)、Ce(2)、Sm(3)、Er(4)](oba=4,4'-二羧基二苯基醚),利用元素分析、红外光谱和粉末X射线衍射等技术手段对其结构及组成进行了表征,热重分析表明,4例配合物具有良好的热稳定性。采用微量热法,实时跟踪监测4种目标配合物对藤黄微球菌的抑制作用,得到了热谱曲线。依据热动力学模型对热谱曲线进行解析,计算了生长和抑制过程的热动力学函数,在不同浓度配合物存在时,获得了细菌生长速率常数(k)、最大产热功率(P_(max))、传代时间(t_G)以及抑制率(I)等参数。结果表明,4种配合物对藤黄微球菌均具有抑制作用,抑菌效果依次为:[Er_2(oba)_3(H_2O)_5]·H_2O(4)[Sm_2(oba)_3(H_2O)_5]·H_2O(3)[Ce_2(oba)_3(H_2O)_5]·H_2O(2)[La_2(oba)_3(H_2O)_5]·H_2O(1)。