KAl（SO4）2·12H2O catalyzed efficient synthesis of 3,4,6-trisubstituted 2-pyridone in water

An efficient green protocol for the preparation 3,4,6-trisubstituted 2-pyridone of employing a condensation reaction of cyanoacetamide and acetylacetone in the presence of KAl（SO₄）₂·12H₂O in water has been described.The present procedure offers advantage such as shorter reaction time,simple workup,and excellent yields.     

Two Alkali Metal Germanophosphates Na3[Ge(OH)(PO4)2]·2H2O and Li2Na[GeO(HPO4)(PO4)]:Crystal Structures and Thermal Stability

Two new alkali metal germanophosphates,namely,Na₃[Ge(OH)(PO₄)₂]·2 H2 O and Li₂Na[GeO(HPO₄)(PO₄)],have been prepared by solvothermal method,and their crystal structures were determined by single-crystal X-ray diffraction.The title two compounds crystalize in the same orthorhombic space group Pbcm(No.57)and feature similar chain-like structure which is built from zig-zag GeO₆ octahedral thread loop branched by PO₄ tetrahedra.For Na₃[Ge(OH)(PO₄)₂]·2 H₂O,a=10.1650(9),b=13.1975(12),c=6.9751(7)?,V=935.73(15)?³,Z=4,R=0.0356 and wR=0.1109;and for Li₂Na[GeO(HPO₄)(PO₄)],a=6.9855(5),b=14.5809(18),c=6.6620(5)?,V=678.56(11)?³,Z=4,R=0.0286,and w R=0.0762.The partial substitution of Na ions by Li ions not only significantly influences the total structural features and the water molecule contents,but also impacts on their thermal stabilities.Li₂Na[GeO(HPO₄)(PO₄)]is thermally stable up to 400℃,whereas only 150℃ for Na₃[Ge(OH)(PO₄)₂]·2 H2 O.     

ZrOCl2·8H2O catalyzed solvent-free synthesis of isobenzofuran-1（3H）-ones

ZrOCl₂·8H₂O catalyzed environmentally benign synthesis of isobenzofuran-1（3H）-ones are described.ZrOCl₂·8H₂O appeared to be an excellent catalyst for the condensation and reactions.Reaction of phthalaldehydic acid（2-carboxybenzaldehyde） with methylaryl and cyclic ketones was initiated by condensation and occurred in one step providing excellent yields（90-98%）.     

Two New Copper Complexes by H_4AQTC(Anthraquinone-1,4,5,8-tetracarboxylic Acid):Syntheses,Structures and Properties

Two new complexes[Cu(AQTC)_0.5(H₂O)₃]·3H₂O}_n (1,H₄AQTC=anthraquinone-1,4,5,8-tetracarboxylic acid) and Cu[(Py)₂C(OH)₂]₂(H₂AQTC)·2H₂O (2,(Py)₂CO=di-2-pyridyl ketone) have been prepared and characterized by elemental analyses and IR spectroscopy.X-ray crystallographic studies show that complex 1crystallizes in monoclinic space group C2/m and complex 2 in monoclinic space group P2_1/c.Complex 1 features a1D chain structure by carboxyl oxygen atoms.Complex 2 displays a mononuclear structure and anions and cations are separated.What's interesting is that the ligand of H₄AQTC with eight carboxyl oxygen atoms and two quinone oxygen atoms does not directly coordinate with metals,and only exist as a counter-anion in complex 2.Three-dimensional structures of two complexes are formed by intermolecular interactions.The thermogravimetric analyses of two complexes are investigated.The luminescent properties of complex 1 are investigated as well.     

A Robust Heterometallic Cd（Ⅱ）/Ba（Ⅱ）-Organic Framework with Exposed Amino Group and Active Sites Exhibiting Excellent CO2/CH4 and C2H2/CH4 Separation

A microporous and robust bimetal-organic framework [Cd₂Ba（NH₂-BTB）₂]·2（DMA）·2（H₂O）(1) was constructed by mixing the heterometallic nodes and an tridentate carboxyl ligand with amino group, benefiting from the synergistic effect of active sites, exposed amino groups and ultramicroporous structure. This compound displays an extraordinary selectivity of CO₂/CH₄ and C₂H₂/CH₄（16.7 and 146.3） at 298 K an...     

Catalytic conjugate addition of indole toα,β-unsaturated ketones by Co（ClO4）-2·6H2O/bis-Schiff base complexes

Co（ClO₄）)₂·6H₂O/bis-Schiff base complexes promoted the conjugate addition of indole toα,β-unsaturated ketones under mild conditions,giving the corresponding addition products with high yields.And the complex has been characterized with XRD and IR.     

Synthesis,Crystal Structure and Antitumor Activity of a Ca(Ⅱ) Coordination Polymer Based on 4-Acetylphenoxyacetate Ligands

A novel Ca(Ⅱ) coordination polymer,[Ca L₂(H₂O)₂]_n (1,HL=4-acetylphenoxyacetic acid) has been synthesized with 4-acetylphenoxyacetic acid,Ca(ClO_4)₂·4H₂O and Na OH as raw materials.Complex 1 was characterized by elemental analysis and single-crystal X-ray diffraction analysis.The results show that the Ca(Ⅱ)ion is eight-coordinated in a distorted triangular dodecahedral geometric configuration with six carboxylate Oatoms of four L ligands and two O atoms of two coordinated water molecules.Complex 1 forms a one-dimensional chained structure by the bridging effect of carboxylate O atoms.The antitumor activity of HLligand and complex 1 has also been investigated.     

磷酸铁锂废料中FePO4·2H2O提取及其杂质形成机理

采用化学共沉淀方法从磷酸铁锂废料中提取FePO₄·2H₂O,并研究了回收过程中杂质形成的机理。在热力学计算基础上绘制了298和363 K时Fe-P-Li-H₂O体系的电势(φ)-pH图,结果表明当pH≤5.0时,Fe(OH)₃相可以自发地转成FePO₄·2H₂O相,从而得到高纯的FePO₄·2H₂O。但实验结果发现当溶液中铁、磷的物质的量之比(n_Fe∶n_P)为1∶1,合成pH为1.5～2.2时得到的FePO₄·2H₂O中存在Fe(OH)₃杂质,这是因为在共沉淀过程中少量Fe³⁺以Fe(OH)₃快速沉淀,而陈化时Fe(OH)₃相转化速率慢,因此FePO₄·2H₂O中含有Fe(OH)₃     

Two isostructural Ni(Ⅱ)/Co(Ⅱ)-based metal-organic frameworks for selective dye adsorption and catalytic cycloaddition of CO2 with epoxides

Two isostructu ral Ni(Ⅱ)/Co(Ⅱ)-based metal-organic frameworks(MOFs),namely {[M₃(L)₂(bpb)₃(H₂ O)₄]·2 DMF·2 H₂O}_n [M=Ni(HL-5,HL is short for Hui-Ling Liu);M=Co(HL-6);H₃ L=2',6'-dimethyl-[1,1'-biphenyl]-3,4',5-tricarboxylic acid;bpb=1,4-bis(pyrid-4-yl)benzene],have been hydrothermally synthesized and structu rally characterized.Both HL-5 and HL-6,which have the same three-interpenetrated3 D pillared-layer framework with sqc306 type topology,present good selective methyl orange(MO)adsorption over rhodamine B(RhB).Moreover,the catalytic CO₂ cycloaddition properties with epoxides of the two MOFs have also been studied at ambient pressure and temperature.     

三维化合物[Ni2(BDC)2(m-bix)(H2O)3·3H2O]n的合成、结构和性质

水热条件下,合成了一个三维配位聚合物[Ni₂(BDC)₂(m-bix)(H₂O)₃·3H₂O]_n(1)[BDC=对苯二甲酸,m-bix=1,3-双(咪唑基-1-甲基)-苯],并通过红外,热重和X-射线单晶衍射进行了表征。X射线衍射结果表明化合物含有类似配位环境的金属2个Ni²⁺离子,2个BDC^2-配体,1个m-bix分子,3个配位水分子和3个游离的溶剂水分子。两个Ni²⁺离子分别采用八面体构型,通过桥联水分子形成双核单元,然后通过全部脱质子的BDC形成三维孔洞结构,m-bix配体通过连接两类双核金属原子形成三维框架,游离水分子存在于框架之中。有趣的是,化合物的结构是单一六节点,具有自穿插特征。而且对化合物的红外和热重性质进行了表征。     

The electrolyte NRTL model and speciation approach as applied to multicomponent aqueous solutions of H2SO4, Fe2(SO4)3, MgSO4 and Al2(SO4)3 at 230–270 °C

This work presents chemical modeling of solubilities of metal sulfates in aqueous solutions of sulfuric acid at high temperatures. Calculations were compared with experimental solubility measurements of hematite (Fe₂O₃) in aqueous ternary and quaternary systems of H₂SO₄, MgSO₄ and Al₂(SO₄)₃ at high temperatures. A hybrid model of ion-association and electrolyte non-random two liquid (ENRTL) theory was employed to fit solubility data in three ternary systems H₂SO₄–MgSO₄–H₂O, H₂SO₄–Al₂(SO₄)₃–H₂O at 235–270 °C and H₂SO₄–Fe₂(SO₄)₃–H₂O at 150–270 °C. Employing the Aspen Plus™ property program, the electrolyte NRTL local composition model was used for calculating activity coefficients of the ions Al³⁺, Mg²⁺ Fe³⁺ and SO₄²⁻, HSO₄⁻, OH⁻, H₃O⁺, respectively, as well as molecular species. The solid phases were hydronium alunite (H₃O)Al₃(SO₄)₂(OH)₆, hematite Fe₂O₃ and magnesium sulfate monohydrate (MgSO₄)·H₂O which were employed as constraint precipitation solids in calculating the metal sulfate solubilities. A correlation for the equilibrium constants of the association reactions of complex species versus temperature was implemented. Based on the maximum-likelihood principle, the binary interaction energy parameters for the ionic species as well as the coefficients for equilibrium constants of the reactions were obtained simultaneously using the solubility data of the ternary systems. Following that, the solubilities of metal sulfates in the quaternary systems H₂SO₄–Fe₂(SO₄)₃–MgSO₄–H₂O, H₂SO₄–Fe₂(SO₄)₃–Al₂(SO₄)₃–H₂O at 250 °C and H₂SO₄–Al₂(SO₄)₃–MgSO₄–H₂O at 230–270 °C were predicted. The calculated results were in excellent agreement with the experimental data.     

Solid state photodecomposition studies of K4Ti(O2)4·2H2O, K3Ta(O2)2F4 and K2V2O3(O2)2F2

The compounds K₄Ti(O₂)₄·2H₂O, K₃Ta(O₂)₂F₄ and K₂V₂O₃(O₂)₂F₂ undergo photolysis in the solid state. The photolysis kinetics obey the parabolic rate equation p = kt^1/2 and indicate a monoexcitation process for the photolysis. These features are similar to those reported previously for peroxo complexes. The mechanism of evolution of oxygen reported earlier appears to be the same in all these solids.     

Optical spectroscopy of chromium doped (CH3)2NH2X(SO4)2·6H2O (X=Al, Ga) single crystals

Chromium doped (CH₃)₂NH₂Al(SO₄)₂·6H₂O (DMAAlS) and (CH₃)₂NH₂Ga(SO₄)₂·6H₂O (DMAGaS) single crystals were grown and investigated using the methods of optical spectroscopy. It was found that the Cr³⁺ ions in the two crystals are situated in a strong crystal field in which the ²E state is the lowest. The single narrow R-line associated with the ²E–⁴A₂ phosphorescence of Cr³⁺ in DMAAlS in a ferroelectric phase indicates an undistorted octahedral site, whereas important distortion of O_h symmetry and structural disorder was inferred from spectral data obtained with DMAGaS:Cr³⁺ in a low temperature phase. Results of optical investigation are discussed taking into account the structural data.     

Hydrothermal synthesis, crystal structure and characterization of [Zn(H2O)4]2 [H2As6V15O42(H2O)]·2H2O

The compound [Zn(H₂O)₄]₂[H₂As₆V₁₅O₄₂(H₂O)]·2H₂O (1) has been synthesized and characterized by elemental analysis, IR, ESR, magnetic measurement, third-order nonlinear property study and single crystal X-ray diffraction analysis. The compound 1 crystallizes in trigonal space group R3, a=b=12.0601(17) Å, c=33.970(7) Å, γ=120°, V=4278.8(12) Å³, Z=3 and R1(wR2)=0.0512 (0.1171). The crystal structure is constructed from [H₂As₆V₁₅O₄₂(H₂O)]⁴⁻ anions and [Zn(H₂O)₄]²⁺ cations linked through hydrogen bonds into a network. The [H₂As₆V₁₅O₄₂(H₂O)]⁶⁻ cluster consists of 15 VO₅ square pyramids linked by three As₂O₅ handle-like units.     

Structural and spectroscopic properties of Hexamethylenetetramine cobalt(II) complex: [Co(NCS)2(hmt)2(H2O)2][Co(NCS)2(H2O)4] (H2O)

Synthesis, structure, spectroscopy and thermal properties of complex [Co(NCS)₂(hmt)₂(H₂O)₂][Co(NCS)₂(H₂O)₄] (H₂O) (I), assembled by hexamethylenetetramine and octahedral Co(II) metal ions, are reported. Crystal data for I: F_w 387.34, a=9.020(8), b=12.887(9), c=7.95(1) Å, =96.73(4), β=115.36(5), γ=94.16(4)°, V=820(1) Å³, Z=2, space group=P−1, T=173 K, λ(Mo-K)=0.71070 Å, ρ_calc=1.718567 g cm⁻³, μ=17.44 cm⁻¹, R=0.088, R_w=0.148. An interesting two-dimensional network is assembled via hydrogen bonds through coordinated and free water molecules. The d–d transition energy levels of Co(II) ion are determined by UV–vis spectroscopy and calculated by ligand field theory. The calculated results agree well with experiment ones.     

Syntheses and X-ray crystal structures of [Co(η-CO3)(NH3)4](NO3)·0.5H2O and [(NH3)3Co(μ-OH)2(μ-CO3)Co(NH3)3][NO3]2·H2O

[Co(η²-CO₃)(NH₃)₄](NO₃)·0.5H₂O and [(NH₃)₃Co(μ-OH)₂(μ-CO₃)Co(NH₃)₃][NO₃]₂·H₂O were prepared by prolonged aerial oxidation of a solution of Co(NO₃)₂·6H₂O and ammonium carbonate in aqueous ammonia. The formation of these side products highlights the richness of the chemistry of these systems and the possibility of by products if methods are not strictly adhered to. The X-ray crystal structures of [Co(η²-CO₃)(NH₃)₄][NO₃]·0.5H₂O and [(NH₃)₃Co(μ-OH)₂(μ-CO₃)Co(NH₃)₃][NO₃]₂·H₂O reveal a monomeric octahedral cobalt center with η²-bound CO₃²⁻ in the former, while the latter consists of a dimeric array where the two cobalt centers are bridged by two OH⁻ and one μ₂-CO₃²⁻ groups with three terminal NH₃ ligands for each Co center. In both complexes extensive hydrogen bonding interactions are evident.     

CRYSTAL STRUCTURE OF A HETERONUCLEAR LANTHANIDE COMPLEX OF ERBIUM-YTTRIUM AND GLYCINE[ErY(GlY)_6(H_2O)_4](ClO_4)_65H_2O

The title complex [ErY(Gly)_6(H_2O)_4](ClO_4)_6 5H_2O has been synthesized.Its crystalstructure has been determined by X-ray diffraction method.The crystal is triclinic with space groupP1.The unit cell parameters are as follows:a=11.518(4),b=14.105(7),c=15.530(6) ,α=96.61(3),β=102.74(3),γ=105.70(3)°,V=2327.7(17) ~3,Z=2,Dc=2.091g/cm~3.The structure has been refinedto a final R of 0.0785.The crystal is an infinite chain complex,in which four carboxyl groups fromglycine molecules bridge the Er(Ⅲ)and Y(Ⅲ)ion,other two carboxyl groups bridge two adjacentEr(Ⅲ)or two Y(Ⅲ)ions.     

H_2O对SO_2在CaO表面上吸附的影响理论研究

采用密度泛函理论研究了H_2O对SO_2在CaO(001)表面上吸附的影响。结果表明,以四种形式(-H_2O、-H、-OH和-H-OH)存在的H_2O使SO_2在CaO表面上的吸附构型发生改变。SO_2在不同形式H_2O基团邻位吸附时,-H使S原子的p轨道态密度峰明显左移且吸附能比洁净表面大90 kJ/mol,其余基团表面吸附能无明显变化;SO_2吸附于-OH和-H-OH生成HSO_3基团,吸附能相比于洁净表面较小,可能作为暂态结构;SO_2吸附于-H_2O生成SO_3基团,H_2O断键生成的H基团起主要吸附作用,CaO表面上生成类似Ca(OH)_2的局部结构且吸附能比洁净表面大45 kJ/mol。     

Synthesis and molecular structure of Ba5(μ5-OH)[μ3-OCH(CF3)2]4[μ2-OCH(CF3)2]4 [OCH(CF3)2](THF)4(H2O)·THF: a source of barium fluoride

The reaction between metallic barium and fluoroisopropanol or alcoholysis of [Ba(OPrⁱ)₂] produces a pentanuclear fluoroalkoxide. Its X-ray structure determination showed its formulation to correspond to Ba₅(μ₅-OH)[μ₃-OCH(CF₃)₂]₄[μ₂-OCH(CF₃)₂]₄ [OCH(CF₃)₂](THF)₄(H₂O)·THF. The metallic core is based on a square pyramid encapsulating an hydroxo ligand. In addition to the barium---alkoxide bonds [2.53(3)–2.86(3) Å] neutral O-donors, four THF [2.82(2)–2.86(3) Å] and one H₂O [2.79(3) Å] and secondary barium---fluorine interactions [2.99(2)–3.31(2) Å] ensure high coordination numbers, from 9 to 11 for the metal centers. Hydrogen bonding between the apical fluoroisopropoxide, the water molecule and one THF molecule, non-bonded to a metal center, accounts for the stability of the hydrate and illustrates the Lewis acidity of fluoroalkoxides. Thermal decomposition leads to BaF₂.     

Nd(Gly)2Cl3·3H2O和Pr(Ala)3Cl3·3H2O的热力学性质

利用精密自动绝热热量计测定了Nd(Gly)₂Cl₃·3H₂O在80-357K和Pr(Ala)₃Cl₃·3H₂O在80-374K温区的热容. 根据两个化合物的热容计算出了相对于参考温度298.15K的热力学函数(H_T?H_298.15)和(S_T?S_298.15). 根据热重(TG)分析结果, 提出了这两个稀土化合物可能的热分解机理. 利用溶解-反应恒温热量计测定相关化合物的溶解焓并设计盖斯热化学循环, 计算出了两个化合物的标准摩尔生成焓.