新型层状磷酸铝[Al6P8O32][(C2H5)2NHCH2CH2NH3]2·[C2H5NH2CH2CH2NH2C2H5] 的合成、表征及其共模板作用

在溶剂热体系中,以N,N-二乙基乙二胺为结构导向剂,合成了Al/P为3/4的层状磷酸铝[Al6P8O32][(C2H5)2NHCH2CH2NH3]2·[C2H5NH2CH2CH2NH2C2H5]单晶,并通过X射线单晶衍射结构分析.XRD,ICP,元素分析,差热-热重分析等手段进行了表征.该化合物属单斜晶系,P2(1)/c空间群,晶胞参数:a=0.90945(2)nm,b=1.46424(4)nm,c=1.87572(5)nm,β=102.672(2)°,Z=4.其阴离子层由AlO4四面体和PO3(=O)四面体单元交替连接构成,形成四、六、八元环拓扑结构,无机层以ABAB方式堆积,两种质子化的有机胺分子N,N-二乙基乙二胺及其重排产物N,N′-二乙基乙二胺填充在层间.用分子动力学模拟方法,考察了标题化合物中有机胺与无机层间的相互作用,讨论了这两种有机胺的共模板作用.     

Li2O-TiO2-SiO2-P2O5和Li2O-TiO2-Al2O3-P2O5体系锂离子固体电解质的制备及性能研究

一些具有NASICON型网格结构的固体电解质具有高的电导率和好的稳定性,NASICON的意思是Na Super Ionic Conductor[1]。当NaZr2(PO4)3中P5 被Si4 部分取代时便可以得到具有NASICON结构的Na1 xZr2SixP3-xO12体系,其具有高的钠离子电导率。然而有相同结构的Li1 xZr2SixP3-xO12体系的离子电导率却很低,这是因为Li 半径太小,而NASICON三维网格结构的离子通道太大,两者不匹配而使电导率下降[2]。但当LiZr2(PO4)3中Zr4 被离子半径小些的Ti4 取代,所得LiTi2(PO4)3的通道就与Li 半径相匹配,适合于锂离子的迁移,从而使其电导率…     

[(NH2CH2CH2NH3)2WⅥO2(NHC6H4NH)2]2(NH2CH2CH2NH2)·H2O配合物的合成与晶体结构

Cis-dioxo-tungsten(Ⅵ) complex, (NH₂CH₂CH₂NH₂)[(NH₂CH₂CH₂NH₃)₂W^ⅥO₂(NHC₆H₄NH)₂]₂·H₂O is synthesized at room temperature by the reaction of sodium tungstate with o-phenylenediamine. The crystal structure of complex was determined by X-ray diffraction structural analysis. The results show that complex belongs to monoclinic system with space group P2₁/ c, a=0.712 8(2) nm, b=3.081 1(10) nm, c=0.981 9(3) nm, β=102.615(4)°, V=2.104 4(11) nm³, Z=2, μ=55.26 cm^-1, F(000)=1 176. Compared the complex with its analogous biomimetic complexes of the cofactor of molybdoenzymes and tungstoenzymses, it is found that the variance of the coordination atoms and the metal ions center have no influence on the coordination feature, and exhibits distored octahedral coordination with cis-dioxo o-phenylenediamine. CCDC: 252834.     

Li2SO4-Na2SO4-H2O和Li2SO4- K2SO4-H2O溶液的体积性质

本文用高精度数字式振荡管密度计测定了288K至318K温度范围内Li₂SO₄ + Na₂SO₄ + H₂O和 Li₂SO₄ + K₂SO₄ + H₂O三元体系的密度。混合溶液的离子强度范围从0.1到4.5 mol.kg_–1,混合溶液中Na₂SO₄和K₂SO₄的离子强度分数为0.2,0.4,0.6和0.8。用密度实验值拟合得到了不同温度下Pitzer离子相互作用模型混合参数θ_V和 ψ_V,模型的计算值与实验值的偏差在±0.002 g.cm_–3以内。用Pitzer模型计算了不同离子强度下三元体系的混合体积。     

Solubility in the NaClO3 · 2CO(NH2)2-NH2CH2CH2OH-H2O system

The solubility in the NaClO₃ · 2CO(NH₂)₂-NH₂CH₂CH₂OH-H₂O system was studied over the range from the complete solidification temperature (−54.8°C) to 60°C. A polythermal solubility diagram was constructed where the regions of crystallization of ice, carbamide, sodium dicarbamidochlorate, monoethanolamine dihydrate, monoethanolamine monohydrate, and anhydrous monoethanolamine were demarcated. The system is a simple eutonic.     

Li2O-Na2O-B2O3-SiO2烧结助剂对BaAl2Si2O8陶瓷结构与介电性能的影响

采用传统固相反应工艺,按化学计量比合成BaO-Al_2O3-SiO_2(BAS)-x%(w/w) Li_2O-Na_2O-B_2O3-SiO_2(LNBS)(x=0,1,2,3,4)陶瓷。研究不同LNBS烧结助剂添加量对BAS系微波介质陶瓷的结构和介电性能的影响。通过Clausius-Mossotti公式计算讨论了BAS理论与实验介电常数(εr)的差异。研究结果表明:LNBS烧结助剂中Li+进入钡长石Al3+位或单四元环(S4R)间隙,并产生了O_2-空位或Ba2+空位,从而促进BAS六方相向单斜相的转变。添加适量的LNBS烧结助剂后,BAS陶瓷的烧结温度从1 400℃降低到1 325℃,同时BAS陶瓷样品密度、品质因数(Qf)值以及频率温度系数(τf)得到改善。当x=1,烧结温度为1 325℃时,可获得综合性能相对较好的BAS陶瓷,其介电性能:Qf=35 199 GHz,εr=6.37,τf=-1.613×10-5℃-1。     

SO2F2/H2O2/碱和硫醚的氧化反应

考察了一种新型高效的氧化体系SO₂F₂/H₂O₂/碱应用于硫醚的氧化反应,结果以良好到优秀的收率生成了相应的产物砜.对该反应中碱和溶剂进行了优化,确定了最优的反应条件.对底物普适性进行了研究,实验结果表明该氧化体系显示了良好的官能团耐受性.该氧化体系的一个突出的优点是,所使用的试剂都为无机物,反应后副产物为易溶于水的无机盐和水,后处理时易于除去,从而大大简化了产物的分离和纯化.     

富勒烯配合物C60Pd(Ph2PCH2CH2CH2CH2PPh2)的合成和光电性能

本文在惰性气氛中通过取代反应合成出富勒烯金属配合物C₆₀Pd(Ph₂PCH₂CH₂CH₂CH₂PPh₂)，采用元素分析、红外光谱、紫外可见光谱、光电子能谱以及X射线粉末衍射等手段对产物进行表征,同时研究了产物的氧化还原性能及热稳定性能。此外，在光电化学电池中测定了C₆₀Pd(Ph₂PCH₂CH₂CH₂CH₂PPh₂)在GaAs电极上形成n+n型异质结的光伏效应，结果表明：产物具有优良的光电转化性能，尤其是在BQ/H2Q介质电对中，光生电压最大达到212 mV；当C₆₀Pd(Ph₂PCH₂CH₂CH₂CH₂PPh₂)薄膜厚度为1 μm时，光伏效应值最大。     

分步沉淀对CeO2-ZrO2-Y2O3-La2O3材料热稳定性的影响

研究了传统沉淀法和分步沉淀对CeO₂-ZrO₂-Y₂O₃-La₂O₃(CZ)材料结构和性能的影响. N₂-吸/脱附、 OSC、 H2-TPR和催化剂三效活性等测试结果表明:分步沉淀所制备的CZ材料表现出更优的氧化还原性能和织构性能.基于此,继续优化分步沉淀中晶种的含量(10%、 50%、 90%),结果表明:较少的晶种诱导可以极大程度提高材料热稳定性能和织构性能,但进一步增加晶种含量对材料热稳定性能提升作用不明显.其中,当晶种量为10%时,所得CZ材料在高温焙烧后仍保持最大比表面积及稳定的立方相结构,表现出最好的织构性能和热稳定性能,其负载的单Pd三效催化剂也因此表现出最优的三效催化活性.     

P2O5对Li2O-SiO2-Al2O3-K2O-ZnO体系微晶玻璃析晶性能的影响

采用差热分析、X射线衍射及扫描电镜分析手段研究了P₂O₅对Li₂O-SiO₂-Al₂O₃-K₂O-ZnO体系牙科微晶玻璃析晶性能的影响, 并确定了P₂O₅的最适含量. 结果发现P₂O₅是该玻璃体系的有效成核剂, 未添加P₂O₅的玻璃体系成核密度低, 热处理后不能形成微晶体, 且主晶相为硅酸锂; 添加P₂O₅使玻璃在热处理后形成以二硅酸锂为主晶相的微晶玻璃. 该玻璃体系中添加4.5 wt%的P₂O₅可以得到较高体积含量和理想显微结构的牙科二硅酸锂微晶玻璃. P₂O₅含量为6 wt%的基质玻璃发生乳浊, 呈不透明的乳白色.     

Complexes of zinc,cadmium and mercury(II) with the zwitter-ionic form of NN′-ethylenebis (salicylideneimine)

The Schiff base NN′-ethylenebis(salicylideneimine), H₂ salen reacts with hydrous and anhydrous Zinc, Cadmium and Mercury(II) salts to give complexes M(H₂ salen)X₂·nH₂O (M = Zn, Cd, Hg; XCl, Br, I, NO₃; MZn, X₂SO₄; n = 0?2). Spectroscopic and other evidence indicated that; (i) halide and sulphate are coordinated to the metal ion, whereas the nitrate group is ionic in mercury nitrate compound and covalently bonded in zinc and cadmium nitrato complexes, (ii) the Schiff base is coordinated through the negatively charged phenolic oxygen atoms and not the nitrogen atoms, which carry the protons transferred from phenolic groups on coordination, (iii) therefore the coordination numbers suggested are 4-, in mercury and 4- or 6- in zinc and cadmium Schiff base complexes.     

单N-乙酸取代O_2N_2大环配体及其稀土配合物的合成与表征

近年来,带电离官能团取代的大环成为大环化学研究的热点之一 [1～ 3]。这类大环除了环的腔径及环上配位原子种类对不同离子具有配位选择性外,其电离官能团的酸碱效应,也产生对 pH敏感的配位选择性。另外,由于大环骨架的相对刚性,刚柔相济的作用还起到提高配位能力,改进选择性的效果。迄今为止,人们对全氮取代的氮杂大环及其配合物作了相当深入的研究 [4～ 6],部分氮取代的氮氧杂大环及其配合物的研究还很少 [7,8]。从研究配体配位性能的观点来看,改变大环上氮取代的电离官能团数目可以进一步开发出具有良好选择性的配体。本文报道…     

Cobalt(II) complexes of 1,2-(diimino-4′-antipyrinyl)ethane and 4-N-(4′-antipyrylmethylidene)aminoantipyrine

Cobalt(II) complexes of the Schiff bases 1,2-(diimino-4-antipyrinyl)ethane (GA) and 4-N-(4-antipyrylmethylidene)aminoantipyrine (AA) have been prepared and characterised by elemental analysis, electrical conductance in non-aqueous solvents, i.r. and electronic spectra, as well as by magnetic susceptibility measurements. The complexes have the general formulae [Co(GA)X]X (X = ClO^– ₄ or NO₃ ^–), [Co(GA)X₂] (X = Cl^–, Br^– or I^–), [Co(AA)₂]X₂ (X = ClO₄ ^–, NO₃ ^–, Br^– or I^–) and [Co(AA)Cl₂]. GA acts as a neutral tetradentate ligand, coordinating through both carbonyl oxygens and both azomethine nitrogens. In the perchlorate and nitrate complexes of GA one anion is coordinated in a bidentate fashion, whereas in the halide complexes both anions are coordinated to the metal, generating an octahedral geometry around the Co ion. AA acts as a neutral bidentate ligand, coordinating through the carbonyl oxygen derived from the aldehydic moiety and the azomethine nitrogen. Both anions remain ionic in the perchlorate, nitrate, bromide and iodide complexes of AA, whereas both anions are coordinated to the metal ion in the chloride complex, resulting tetrahedral geometry around the Co ion.     

Coordination Chemistry of Acrylamide 4. Crystal Structures and IR Spectroscopic Properties of Acrylamide Complexes with CoII,NiII, and ZnII nitrates

Acrylamide complexes of metal nitrates: [M(O‐OC(NH₂)CHCH₂)_n(H₂O)_m][NO₃]₂ (M = Co( 1 ), Ni( 2 ) (n = 6 and m = 0) and Zn( 3 ) (n = 4 and m = 2)) have been determined by using single crystal X‐ray diffraction analysis. All complexes crystallize in the triclinic space group . The structures of 1 and 2 represent octahedral species [M(AAm)₆]²⁺ (AAm = O‐OC(NH₂)CHCH₂ and M = Co or Ni) and uncoordinated nitrate ions. The structure of 3 involves the octahedral cation [Zn(AAm)₄(H₂O)₂]²⁺ in which the Zn²⁺ environment includes oxygen atoms of four acrylamide and two water molecules that are stabilized using ionic nitrate ions. The observations of the solid‐state IR spectroscopic vibrational frequencies of these acrylamide complexes are in agreement with the crystal structures.     

Complexes of lanthanide nitrates with 2-N-(6-picoIyl)-benzamide

New complexes of lanthanide nitrates with 2-N-(6-picolyl)-benzamide of the formulae Ln₂[6-pic-BA], [NO₃l₆ (Ln = Y and La-Yb) have been prepared and characterised by chemical analysis, infrared, molar conductance and electronic spectral data. Molar conductance data along with IR data point to the presence of co-ordinated nitrate groups. IR spectra prove the bidentate co-ordination of the ligand to the metal ion, through the oxygen of the secondary amide and the nitrogen of the heterocyclic ring. Electronic spectral studies in the visible region suggest an eight co-ordinate geometry around the metal ions.     

Influence of heterocycles arrangement in structural isomeric ligands on coordination sphere of copper(II) complexes: Crystal structures and spectroscopic characterization

New copper complexes with two structural isomeric ligands, 2-(indazol-1-yl)-2-thiazoline (TnInA) and 2-(indazol-2-yl)-2-thiazoline (TnInL), have been synthesized and characterized by magnetic measurements, IR, electronic and EPR spectroscopies. Moreover, the molecular structures of [Cu(NO₃)(TnInA)₂(H₂O)](NO₃) · (H₂O) (1) and [Cu(NO₃)₂(TnInL)(H₂O)] (2) have been resolved by single-crystal X-ray diffraction studies. In compound 1 the copper ion is in a distorted octahedral geometry, with the equatorial plane formed by four nitrogen donor atoms from two organic ligands and the axial positions occupied by two oxygen atoms from a water molecule and a mono-coordinated nitrate anion. The coordination geometry around the copper atom in compound 2 can be described basically as a square pyramid with two nitrogen atoms from TnInL ligand, one oxygen atom from a water molecule and one oxygen atom from a nitrate group in the equatorial plane. The axial position is occupied by one oxygen atom from a nitrate group. Likewise, a second oxygen atom from the last nitrate group in equatorial position might involve in a weak sixth coordination position to give a (4 + 1 + 1^∗) coordination mode.     

Reaction paths of the formation and consumption of nitroorganic complex intermediates in the selective catalytic reduction of nitrogen oxides with propylene on zirconia-pillared clays according to in situ spectroscopic data

It was found that the adsorption and catalytic properties of nanosized ZrO₂ particles as the pillar constituents of ZrO₂-pillared clay and bulk ZrO₂ are essentially different. The interaction of NO with the surface of bulk ZrO₂ resulted in the formation of three types of nitrate complexes. Only two nitrate species were formed on ZrO₂-pillared clay (the monodentate species was absent). Only an acetate complex was formed in the interaction of a mixture of propylene and oxygen with the surface of bulk ZrO₂, whereas an isopropoxide complex was the main propylene activation species on ZrO₂-pillared clay. On the surface of ZrO₂-pillared clay, isopropoxide and nitrate intermediates formed a complex structurally similar to adsorbed dinitropropane. On the surface of bulk ZrO₂, acetate and monodentate nitrate complexes formed a complex structurally similar to adsorbed nitromethane. The dinitropropane complex on ZrO₂-pillared clay was consumed in reactions with surface nitrates. The decomposition reaction of a dinitropropane compound with the formation of acetate complexes and ammonia predominated on the surface containing no nitrate complexes in the absence of NO + O₂ from a gas phase. The found differences in reactant activation species and their thermal stabilities explained differences in the activities of bulk ZrO₂ and nanosized ZrO₂ particles as pillars in pillared clay in the course of the selective catalytic reduction of nitrogen oxides with propylene in an excess of oxygen.     

Cu(II) complexes of N-propyl-2-picolinamine N-oxide

Cu(II) complexes have been prepared with N-propyl-2-picolinamine N-oxide(PA) employing the perchlorate, tetrafluoroborate, nitrate, chloride and bromide salts. The following unique solids have been isolated and characterized: Cu(PA)₂X₂ (X = ClO₄^?, BF₄^? and NO₃^?) and Cu(PA)X₂ (X = Cl^?, Br^?). Characterization has been accomplished primarily by IR, electronic and ESR measurements of the solid state since considerable alteration of the complexes occurs on dissolution. PA bonds as a bidentate ligand via its N-oxide oxygen and amine nitrogen in all of the complexes. Anion coordination occurs in the halogen complexes and the nitrate ions appear to be bound to Cu(II) as monodentate ligands in Cu(PA)₂(NO₃)₂. In addition, there appears to be a rhombic distortion of the CuO₂N₂ chromophore of the perchlorate and tetrafluoroborate solids which is probably due to the steric requirements of the propyl substituents.     

Synthesis,Crystal Structures and Electrochemical Properties of Complexes [M(ImH)4(tfbdc)(H2O)] (M=Co,Ni)

The title complexes [M(ImH)₄(tfbdc)(H₂O)] ( 1 : M=Co; 2 : M=Ni) (ImH=imidazole, tfbdc=2,3,5,6‐tetrafluoroterephthalate) were synthesized by the reaction of M(OAc)₂·4H₂O, H₂tfbdc and ImH in water solution. The complexes were characterized by elemental analysis, IR spectra, thermogravimetric analysis, cyclic voltammetry and X‐ray single crystal structure analysis. Structural analysis reveals that 1 and 2 possess isostructure: monoclinic, P2₁/c, Z=4. M(II) ion in complexes 1 and 2 has a distorted octahedral geometry coordinated by one oxygen atom from water, one oxygen atom from tfbdc^2? and four nitrogen atoms from ImHs. They are discrete zero‐dimensional molecular complexes. And the adjacent monomeric components are connected by hydrogen bonds to form a supramolecule. Electrochemical properties of the complexes 1 and 2 show that electron transfer of M(II) between M(III) in electrolysis is a quasi‐reversible process.     

Copper(II) complexes of 2-(pyrrolidinomethyl)- and 2-(3-pyrrolinomethyl)pyridine N-oxides

Summary This title pyridine N-oxides have been prepared and their copper(II) complexes isolated as perchlorate, tetrafluoroborate and nitrate salts. The ligands coordinatevia both the pyridine N-oxide oxygen and the amine nitrogen to give bis(ligand) complexes for the perchlorate and tetrafluoroborate salts. The nitrate solids have [CuL(NO₃)₂] stoichiometry with monodentate nitrato-ligands. The spectral properties of these complexes are compared to those of N-alkyl-and N,N-dialkyl2-picolinamine N-oxides as well as other 2-substituted pyridine N-oxides.NATO Fellow on leave from Istanbul Medical Faculty, Istanbul University.