Synthesis,structure and characterization of (NH4)2[Cu2(H2O)4(NH3CH2COO)2(NH2CH2COO)2]H2V10O28·6H2O

The decavanadate with a novel glycine–glycinato complex of copper (II) in the cationic part, (NH₄)₂[Cu₂(H₂O)₄(NH₃CH₂COO)₂(NH₂CH₂COO)₂]H₂V₁₀O₂₈·6H₂O (1), has been prepared and characterized by elemental analysis, infrared and EPR spectroscopies. The triplet X band EPR spectrum of powdered sample evidenced magnetic interaction between the Cu(II) atoms in the dimeric unit which is probably realized through the bridging water molecules in this part of the complex. A single crystal X-ray diffraction study revealed that the structure of 1 contains cationic copper complex with a rare Cu(H₂O)₂Cu double bridge. In this cation, a simultaneous bidentate N, O– and monodentate O– coordination of glycine to the same central atom was observed for the first time.     

[C16H33N(CH3)3]3[PO4(WO3)4]催化脂肪酸甲酯环氧化性能

在无酸、无溶剂条件下,以[C₁₆H₃₃N(CH₃)₃]₃[PO₄(WO₃)₄]为反应控制相转移催化剂,研究各因素对脂肪酸甲酯(FAME)环氧化反应的影响。结果表明,水相pH对环氧化反应的影响最大,反应适宜pH为4;适宜反应条件为过氧化氢与脂肪酸甲酯中双键摩尔比为1.05:1,反应温度50～60℃,反应时间5 h。在此反应条件下催化剂循环5次不失活,产品环氧值大于4.0%,碘值小于5 g I·(100 g)^-1。并通过元素分析与红外光谱,研究了催化剂在反应过程中的变化,认为磷钨杂多阴离子的分解是导致催化剂失活的关键原因。     

Crystal Structure and Physicochemical Properties of Two Supramolecular Compounds: (C4H8NH2)4[Mo8O26] and (NH4)Na2[AsIIIMo6O21(O2CCH2NH3)3]·8H2O

Two inorganic–organic hybrid supramolecular compounds based on polyoxometalates formulated as (C₄H₈NH₂)₄[Mo₈O₂₆] (1) and (NH₄)Na₂[As^IIIMo₆O₂₁(O₂CCH₂NH₃)₃]·8H₂O (2) have been synthesized by conventional solution method and characterized by infrared, UV–Vis and single-crystal X-ray diffraction analyses. Thermal analysis was performed to study their thermal stability. The atomic arrangement in compound (1) can be described as inorganic layers built by [Mo₈O₂₆]^4?, pyrrolidinium cations are embedded into layers. The fascinating structural feature of compound (2) is that the glycine molecules are bounded to two edge-sharing Mo centers via their carboxylate functionality leading to functionalized heteropolymolybdate [As^IIIMo₆O₂₁(O₂CCH₂NH₃)₃]^3?, extensive net hydrogen bonds between cations and anions contribute to the crystal packing. The electrochemical behavior of compound (2) has been studied.     

An unusual o-metallated pyridyl dirhodium(II) complex: [Rh2{μ-(C5H3N)NH(C5H4N)}2{η2-(C5H4N)NH(C5H4N}2]Cl2·CH3OH

Reaction of Rh₂(O₂CMe)₄ and bis(2-pyridyl)amine, Hdpa, followed by addition of CH₂Cl₂ led to replacement of the acetate groups by Hdpa and orthometallation of two Hdpa pyridyl groups. The isolated complex, [Rh₂{μ-(C₅H₃N)NH(C₅H₄N)}₂{η²-(C₅H₄N)NH(C₅H₄N}₂]Cl₂ (1), has been characterized by X-ray crystallography, showing that the complex has two equatorially bound Hdpa groups and two bridging orthometallated dpa anions.     

Synthesis and nanostructure of [Mo(C6H4O2)3]·2(C4H8N2O) and the synthesis from 1,2-PDA to (C4H8N2O)

Continuing our work on the synthesis of MoO₂L₂ and MoO₃L_AL_B that show excellent anti-cancer activities in vitro, the MoL₃ have been synthesized by the solvothermal reaction of Na₂MoO₄ with catechols and 1,2-DPA in the mixed solvent of MeCN/MeOH. X-ray diffraction revealed that Mo in chiral octahedral geometry coordinate with three catechol ligands formed three five-membered rings, and the [Mo(C₆H₄O₂)₃] are linked by hydrogen bonds Mo(OC₆H₄)O…H–N(C₄H₈O)N–H…O(C₆H₄O)Mo through the by-product (C₄H₈N₂O) that are formed by one 1,2-DPA with one CO₂ on the catalysis of Mo-complex. Also, we have disassembled bulk crystal into nano-aggregates, and under TEM mono-lamella morphology of nanostructures was observed, which agrees well with the previous conclusion that the morphologies of the nano-aggregates are associated with the quantum motifs in their crystal lattices. [Mo(C₆H₄O₂)₃] have also been characterized by UV–vis spectra, cyclic voltammogram and thermogravimetric analysis.     

配合物[Co(C6H4O2N)2(H2O)4]的合成与晶体结构

采用水热法,用氯化钻与异烟酸反应得到了分子式为[Co（C6H4O2N）2（H2O）4]的配合物,通过X-射线单晶衍射研究了其结构。该配合物的晶体属三斜晶系,空间群P-1,晶胞参数a=0．63736（19）nm,b=0．6921（2）nm,c=0．9282（3）nm,α=96．051（3）°,β=104．703（3）°,γ=0．113084（3）°,V=0．35454（18）nm^3,Z=1,Dc=1．757g／cm^2,Mr=375．20,F（000）=193,μ（MoKa）=1．257mm^-1,R1=0．0834,wR2=0．2302[I〉2σ（I）],晶体由具有六配位的畸变八面体结构的两性离子通过氢键和面．面π-π堆积构成。     

[PdCl2(NH2(CH2)12CH3)2] supported on γ-Al2O3 as catalyst for selective hydrogenation

The [PdCl₂(NH₂(CH₂)₁₂CH₃)₂] complex supported on -Al₂O₃ has proved to be a considerably more active, selective and sulfur-resistant catalyst in the selective hydrogenation of styrene to ethylbenzene than a traditional catalyst obtained from acid solutions of PdCl₂, and even than the same complex unsupported. The active species is the complex itself and it is stable under the reaction conditions. Hydrogen treatments above 353K destroy the complex, at least partially, leading to a less active and sulfur resistant catalyst. The higher sulfur resistance, when compared to a conventional Pd/Al₂O₃ catalyst, can be attributed to electronic and geometrical effects.     

A new polymeric chain in the dihydrogendecavanadate(V)–decavanadate(V) [NH2(CH2)4]5[V10O28H2]0.5[V10O28]0.5 obtained by in situ synthesis of the organic cation

A new polymeric compound, [NH₂(CH₂)₄]₅[V₁₀O₂₈H₂]_0.5[V₁₀O₂₈]_0.5, was obtained by in situ synthesis of the organic cation from an aqueous solution of V₂O₅–HCl–NH₂(CH₂)₄NH₂. The crystal structure was solved by single-crystal X-ray diffraction. [NH₂(CH₂)₄]₅[V₁₀O₂₈H₂]_0.5[V₁₀O₂₈]_0.5 consists of dihydrogendecavanadate(V), [H₂V₁₀O₂₈]^4?, and decavanadate(V), [V₁₀O₂₈]^6?, units assembled in one-dimensional arrays by interanionic hydrogen bonds O–H?O and cation-anion N–H?O interactions. The latter involve pyrrolidinium cations, which were obtained in the compound instead of the starting butane-1,4-diamine. Pyrrolidinium cations further connect the polymeric chains into a three-dimensional network. The presence of the two types of units, [H_nV₁₀O₂₈]^(6?n)? with n = 0 and n = 2, in one compound was not yet observed and is herein reported for the first time.     

A solvothermal synthesis of a novel 1D ladder-like (NH3CH2CH2NH3)AgAsS4 containing N–H⋯S hydrogen bonding

A one-dimensional compound (NH₃CH₂CH₂NH₃)AgAsS₄ with ladder-like chains was synthesized solvothermally. This compound crystallizes in the monoclinic system, space group C2/c, with a=13.5805(8) Å, b=6.5331(3) Å, c=22.7711(9) Å, α=90°, β=106.42(3)°, γ=90°, Z=8. The rare type hydrogen bonding of N–H⋯S and electrostatic force hold the anionic chains together.     

配合物[Ni(C6H4O2N)2(H2O)2]的合成及晶体结构

采用溶剂热法,用4-羧基吡啶和醋酸镍,合成了一个新的化合物[Ni(C6H4O2N)2(H2O)2],配合物中HC6H4O2N为4-羧基吡啶,并通过单晶体衍射测定了其结构.结构测定表明,该标题配合物属三斜晶系,空间群Pī,晶胞参数为a=6.3070(10)A.,b=6.9310(11)A.,c=9.2770(14)A.;α=96.313(2)°,β=105.189(2)°,γ=113.359(3)°,V=348.67(9)A.3,Z=1,Dc=1.786 g·cm-3,F(000)=194,μ=1.439 mm-1,λ(MoKα)=0.71073A.,Mr=374.98. 最终偏差因子(对I>2σ(I)的衍射点)R1=0.0783,ωR2=0.2055,对全部衍射点R1=0.0819,ωR2=0.2104,ω-1=[s2(F0)2+(0.1832P)2+ 0.0000P],P=(F02+2Fc2)/3.配合物分子中,中心离子Ni(Ⅱ) 采用六配位,6个配原子中,4个氧原子分别来自4个配位水,2个氮分别来自2个4-羧基吡啶,形成一个稍变形的具有对称中心的八面体结构.邻近配合物分子间通过4-羧基吡啶和配位水之间大量的氢键堆积成无限三维网状结构.     

Single crystal structure of a two-dimensional framework: [{Co(4,4′-bpy)(HO3PCH2CH2CH2CH2PO3H)(H2O)2}·4H2O]n

The structure of [{Co(4,4^′-bpy)(HO₃PCH₂CH₂CH₂CH₂PO₃H)(H₂O)₂}·4H₂O]_n 1 was determined by single crystal X-ray diffraction. Compound 1 contains a new two-dimensional framework layer, which is built up from parallelogram units in bc plane. The layers are constructed into a three-dimensional structure by interlayer hydrogen bonds.     

混合配体配合物[Co3(BTC)2(Lb)2(CH3CH2OH)2·4H2O]n的合成与晶体结构

以1,3,5-均苯三甲酸(H3BTC)、2-[1-(2-吡嗪基)乙缩醛腙(La)、醋酸钴、为原料采用水热法合成了配合物[Co3(BTC)2(Lb)2(CH3CH2OH)2·4H2O]n(1)(Lb=2-乙酰基吡嗪缩水合肼).配合物晶体属单斜晶系,空间群C2/c.X-射线单晶衍射结果表明:两个Co2+离子与氧原子、氮原子...     

(NH4)3 H4[P(Mo2O7)6]敏化TiO2光催化剂的制备及其光催化性能

以磷钼酸铵为敏化剂,采用固相研磨法合成了磷钼酸铵敏化光催化剂TiO_2-PMoN。通过X射线衍射、红外吸收和紫外-可见吸收光谱法对样品进行表征,以罗丹明B为模拟污染物,评价其光催化活性。结果表明,所得TiO_2-PMoN催化剂为锐钛矿型和金红石型的混合类型,与纯磷钼酸铵相比,TiO_2-PMONH_4光催化剂在(360～850)cm~(-1)的吸收出现了宽化现象,磷钼酸铵敏化使TiO_2在可见光区的吸收增强,吸收边红移,太阳光照射40min,TiO_2-PMoN光催化降解罗丹明B的脱色率为95%。     

A fast route to the potential biological reagent (η5-C5H4COOH)Re(CO)3 from [NH4] [ReO4]

The rhenium carbonyl carboxylic acid (η⁵-C₅H₄COOH)Re(CO)₃ (Re + 1) is readily accesssible in a rapid fashion starting from perrhenate (Re + 7). This complex can be conjugated to amino acids and proteins opening the way to a robust small radiopharmaceutical.     

Organic–inorganic hybrid oxides: Structure and magnetic properties of [{Cu(terpy)}2Mo6O17(H2O)(O3PCH2NH2CH2PO3)2] · H2O,a bimetallic oxide constructed from novel {Mo6O17(H2O)(O3PCH2NH2CH2PO3)2}4− clusters

The hydrothermal reaction of MoO₃, CuSO₄ · 5H₂O, 2,2′:6′:2″-terpyridine (terpy) and bis-N,N-(methylphosphonic acid) amine (H₂O₃PCH₂NHCH₂PO₃H₂) provided blue crystals of the bimetallic oxide [{Cu(terpy)}₂Mo₆O₁₇(H₂O)(O₃PCH₂NH₂CH₂PO₃)₂] · H₂O (1 · H₂O). The three-dimensional structure of 1 is constructed from {Mo₆O₁₇(H₂O)(O₃PCH₂NH₂CH₂PO₃)₂}⁴⁻ clusters linked through {Cu(terpy)}²⁺ subunits. The cluster consists of three pairs of edge-sharing {MoO₆} octahedra linked through corner-sharing interactions into a {Mo₆O₆} ring. One phosphonate ligand spans the diameter of the ring, bridging four molybdenum sites and leaving at a pendant {PO} group at each terminus. The second diphosphonate ligand exploits one {–PO₃} unit to cap the hexamolybdate ring and bridge all six molybdenum sites while the second {–PO₃} terminus bridges two molybdenum sites, leaving a pendant {PO} unit. Crystal data: C₃₄H₄₅Cu₂Mo₆N₈O₃₅P₄: monoclinic, P2₁/n, a = 11.9431(7) Å, b = 17.382(1) Å, c = 27.524(2) Å, β = 90.429(1)°, V = 5713.7(6) Å³, Z = 4, D_calc = 2.270 g cm⁻³, R₁ = 0.0466.