UO22+·nH2O和PuO22+·nH2O(n=2,4,5,6)密度泛函理论研究

首先用密度泛函理论(DFT)方法研究了铀酰和钚酰离子的几何与电子结构,计算结果与实验基本符合,表明DFT方法也能用于含铀和钚重原子的化合物计算.然后对铀酰和钚酰水合离子的几何构型、Mulliken集居数分布以及铀酰(钚酰)与配体水分子的结合能进行计算,计算结果表明UO22+·5H2O和PuO22+·5H2O分别为铀酰和钚酰系列水合离子中最稳定的配合物.     

Thermal transformations of α-H6P2Mo18O62·nH2O heteropolyacid

According to the ³¹P NMR spectroscopy, heteropolyacid (HPA) H₆P₂Mo₁₈O₆₂·nH₂O (P₂Mo₁₈), -isomer of the Dawson structure, transforms upon heating above 80 °C partially (up to 30%) to -isomer, in which both polar groups Mo₃O₁₃ of the heteropolyanion are turned by 60° around the N₃ axis, and partially to -isomer in which only one group is turned. The - and -isomers of P₂Mo₁₈ have been found for the first time. Their transformation into the -isomer occurs upon rehydration in one week in air and in 1 h in an aqueous solution. HPA P₂Mo₁₈ decomposes on heating up to 350 °C to HPA H₃PMo₁₂O₄₀ (PMo₁₂) and a previously unknown phase of the HPMo₆I₂₁ composition, which in its turn decomposes at 375 °C to molybdenyl phosphates and IiI₃. The PMo₁₂ decomposition occurs via two routes to form the same products at temperatures of 400 and 450 °C with corresponding exotherms of IiI₃ crystallization.     

Nb2O5·nH2O as a heterogeneous catalyst with water-tolerant Lewis acid sites

Niobic acid, Nb(2)O(5)·nH(2)O, has been studied as a heterogeneous Lewis acid catalyst. NbO(4) tetrahedra, Lewis acid sites, on Nb(2)O(5)·nH(2)O surface immediately form NbO(4)-H(2)O adducts in the presence of water. However, a part of the adducts can still function as effective Lewis acid sites, catalyzing the allylation of benzaldehyde with tetraallyl tin and the conversion of glucose into 5-(hydroxymethyl)furfural in water.     

Conductivity and Morphology of Composite Solid Electrolytes SnO2· nH2O–Heteropolycompounds

The structure and surface characteristics of SnO₂ · 1.5H₂O and composite materials with heteropolycompounds (HPC) formulated as SnO₂ · 1.5H₂O–HPC (where HPC = (NH₄)₃PW₁₂O₄₀ · nH₂O, (NH₄)₂HPW₁₂O₄₀ · nH₂O, and H₃PW₁₂O₄₀ · nH₂O) are studied by scanning tunneling microscopy. Hydrated tin oxide is characterized by a globular structure which differs substantially from the morphology of composite materials. The conductivity is studied as a function of both the temperature and humidity of environment and the composition of composite materials. For composite materials containing ((NH₄)₂HPW₁₂O₄₀ · nH₂O, the conductivity is shown to vary monotonously with the composition and obey the mixture rule. Introduction of (NH₄)₃PW₁₂O₄₀ · nH₂O to a composite is found to cause an extremely fast conductivity decay, whereas addition of H₃PW₁₂O₄₀ · nH₂O results in the appearance of a plateau on the conductivity vs. composition curve. The explanation given to the phenomena observed is based on the mechanism of protonic transport in heteropolycompounds.     

Synthesis,Crystal Structure and Photoluminescence of [Gd（C6NO2H5）3- （H2O）2]2n·（nH5O2）（nHgCl5）（2nHgCl4）·（2nH2O）

A heterometallic 4f-5d inorganic-organic metaMsonicotinato hybrid [Gd（C6NO2H5）3- （H2O）2]2n·（nH5O2）（nHgCl5）（2nHgCl4）·（2nH2O） 1 has been synthesized via hydrothermal reaction and structurally characterized. Complex 1 crystallizes in the space group C2/c of monoclinic system with four formula units in a cell： a = 24.234（8）, b = 20.816（7）, c = 15.333（3）A , β= 128.091（8）°, V = 6088（3）A^3, C36H47Cl13Gd2Hg3N6O20, Mr = 2260.92, Dc = 2.467 g/cm^3, S = 0.896, μ（MoKα） = 10.331 mm^-1, F（000） = 4216, R = 0.0344 and wR = 0.0629. The crystal structure analysis reveals that the title complex is characteristic of a one-dimensional chain-like structure. Photoluminescent investigation reveals that the title complex displays a broad and intense emission in the green region.     

Synthesis and Structural Characterization of a Novel Coordination Polymer [Cd(C4H2O4)(C3H4N2)3]n·2nH2O

At room temperature, a new three-dimensional organic-inorganic coordination polymer [Cd(C4H2O4)(C3H4N2)3]n·2nH2O was synthesized by the reaction of Cd(CH3COO)2(2H2O, imidazole and fumaric acid. It was characterized by EA, IR, TG-DTA and X-ray single-crystal diffraction. It crystallizes in the monoclinic system, space group P21/n with a = 8.980(3), b = 15.803(5), c = 13.415(4) (A), α = γ = 90.00°, β = 98.450(5)°, F(000) = 936, Mr = 466.73, Z = 4, V = 1883.0(10) (A)3, Dc = 1.646 g/cm3, μ(MoKα) = 1.201 mm-1, S = 1.041, the final R = 0.0237 and wR = 0.0469. The crystal structure shows that the cadmium has a distorted octahedral environment with three carboxyl oxygen donors and three imidazole nitrogen donors. Each cadmium atom is linked by a fumatate as bridging ligand to afford a one-dimensional framework, and then an infinite threedimensional supramolecular network is formed through hydrogen bonding interactions.     

配位聚合物[Ho2(TsGlyH)6(H2O)4]n·4nH2O的水热合成、晶体结构和抑菌活性

采用水热方法合成高氯酸钬与对甲苯磺酰甘氨酸1∶3型配合物[Ho2(TsG lyH)6(H2O)4]n.4nH2O。配合物晶体属三斜晶系,P i空间群,晶胞参数为:a=1.3927(1)nm,b=1.6645(2)nm,c=1.6485(2)nm,α=73.93(8),°β=76.42(1),γ=75.42(1),°V=5.569(7)nm3,Z=2,D c=1.623 mg/m3,M r=1746.04,F(000)=1806,Rl=0.0274,wR2=0.0553。每一个二聚单元[Ho2(TsG lyH)6(H2O)4]中的Ho(III)离子由四个对甲苯磺酰甘氨酸的羧基桥相连,同时二聚单元中的每一个Ho(III)离子再进一步通过另外两个羧基桥与邻近的稀土离子相连,从而构成一维链状结构。     

Synthesis, Crystal Structure, and Photoluminescent and Semiconductive Properties of [La(C6NO2H5)3-(H2O)2]2n·(nH5O2)(nHgCl5)(2nHgCl4)·(2nH2O)

A new heterometallic 4f-5d inorganic-organic metal-isonicotinic acid complex [La(C6NO2H5)3(H2O)2]2n·(nH5O2)(nHgCl5)(2nHgCl4)·(2nH2O) 1 has been synthesized via hydro-thermal reaction and structurally characterized. Complex 1 crystallizes in the space group C2/c of monoclinic system with four formula units in a cell: α= 24.140(7), b = 20.884(7), c = 15.462(2) (A), β = 127.46(1)°,V = 6187(3) (A)3, C36H47Cl13Hg3La2N6O20, Mr = 2224.24, Dc = 2.388 g/cm3, Z = 4, T = 293(2) K, μ(MoKα) = 9.401 mm-1, F(000) = 4160 and R/wR = 0.0376/0.0636 for 4130 observed reflections (I > 2σ(I)) and 5617 unique reflections. Complex 1 is characteristic of a one-dimensional polycationic chain-like structure. Photoluminescent investigation reveals that the title complex displays interesting emissions in violet and orange regions. The luminescence spectra show stronger orange emission than violet emission. Optical absorption spectra of 1 reveal the presence of a wide optical bandgap of 3.41 eV.     

Synthesis,Crystal Structure,and Photoluminescent and Semiconductive Properties of [La（C6NO2Hs）3-（H2O）2]2n·（nH5O2）（nHgCl5）（2nHgCl4）·（2nH2O）

A new heterometallic 4f-5d inorganic-organic metal-isonicotinic acid complex [La（C6NO2Hs）3-（H2O）2]2n·（nH5O2）（nHgCl5）（2nHgCl4）·（2nH2O） 1 has been synthesized via hydro- thermal reaction and structurally characterized. Complex 1 crystallizes in the space group C21c of monoclinic system with four formula units in a cell： a = 24.140（7）, b = 20.884（7）, c = 15.462（2）A, fl = 127.46（1）°, V = 6187（3）A3, C36HaTCl13Hg3La2N6020, Mr = 2224.24, Dc = 2.388 g/cm3, Z = 4, T = 293（2） K, μ（MoKa） = 9.401 mm-1, F（000） = 4160 and RIwR = 0.0376/0.0636 for 4130 observed reflections （I 〉 20（/）） and 5617 unique reflections. Complex 1 is characteristic of a one-dimensional polycationic chain-like structure. Photoluminescent investigation reveals that the title complex displays interesting emissions in violet and orange regions. The luminescence spectra show stronger orange emission than violet emission. Optical absorption spectra of 1 reveal the presence of a wide optical bandgap of 3.41 eV.     

ZnSO4·CO(NH2)2·2H2O和MgCl2·NH4Cl·6H2O的热分解动力学研究

采用TG-DSC研究了ZnSO4·CO(NH2)2·2H2O和MgCl2·NH4Cl·6H2O的热分解反应,并对其中的脱水过程及部分分解过程进行了动力学计算,由Fridman、Ozawa-Flynn-Wall、ASTME698三种方法得出峰温时的活化能值与指前因子值,通过优化选择出了热分解过程最佳机理函数.     

Solubility and Stability of Peroxo Solvates KF·nH2O2 in Organic and Aqueous-Organic Media

The solubility and stability of the peroxo solvates KF·nH₂O₂ (n 1) and disinfectants based on them was studied in organic and aqueous-organic solvents. Polyhydric alcohols (glycerol and ethylene glycol) and Tosol (commercial antifreeze) were used as solvents.     

Thermochemistry of two lead borates; Pb(BO2)2·H2O and PbB4O7·4H2O

Two pure hydrated lead borates, Pb(BO₂)₂·H₂O and PbB₄O₇·4H₂O, have been characterized by XRD, FT-IR, DTA-TG techniques and chemical analysis. The molar enthalpies of solution of Pb(BO₂)₂·H₂O and PbB₄O₇·4H₂O in 1 mol dm^?3 HNO₃(aq) were measured to be (?35.00 ± 0.18) kJ mol^?1 and (35.37 ± 0.14) kJ mol^?1, respectively. The molar enthalpy of solution of H₃BO₃(s) in 1 mol dm^?3 HNO₃(aq) was measured to be (21.19 ± 0.18) kJ mol^?1. The molar enthalpy of solution of PbO(s) in (HNO₃ + H₃BO₃)(aq) was measured to be ?(61.84 ± 0.10) kJ mol^?1. From these data and with incorporation of the enthalpies of formation of PbO(s), H₃BO₃(s) and H₂O(l), the standard molar enthalpies of formation of ?(1820.5 ± 1.8) kJ mol^?1 for Pb(BO₂)₂·H₂O and ?(4038.1 ± 3.4) kJ mol^?1 for PbB₄O₇·4H₂O were obtained on the basis of the appropriate thermochemical cycles.     

L-丙氨酸桥联配位聚合物[Cu2(L-ala)2(phen)2]n· 2nClO4·2nH2O的合成及其结构

The complex, [Cu2(L-ala)2(phen)2]n·2nClO4.2nH2O (L-ala=L-alaninate, phen=1,10-phenanthroline) has been synthesized and investigated by elemental analysis, IR spectroscopy, and X-ray diffraction methods.The complex crystallizes in the monoclinic space group P21 with a=1.1611(4) nm, b=0.717 2(2) nm, c=2.0741(7)nm, β=101.028 (6)°,V = 1.695 4(9) nm3, Dc= 1.760 g. Cm-3, Z=4,μ= 1.493 mm-1, F(000) =916, R =0.052 2, wR =0.1279for 7 131 unique reflections. The cations of [Cu2(L-ala)2(phen)2]n2n+ have an one-dimensional polymeric structure,due to the bridging of two Cu(phen)2+ units by a carboxylate group of L-alaninate, and each Cu(Ⅱ) ion is in a slightly distorted square-pyramidal coordination geometry, with the phen (N,N') and the L-ala (N,O) acting as bidentate ligands in the equatorial plane and another carboxylate oxygen atom from a symmetry-related neighboring Lalaninate ion in the apical position.     

Study of optical properties of highly oriented nanocrystalline V2O5·nH2O films doped with K ions

Optical transmission and reflection measurements of highly oriented nanocrystalline K_xV₂O₅·nH₂O films (0 ≤ x < 0.01) were studied. The optical constants such as, refractive index, the extinction coefficient, absorption coefficient, optical band gap have been calculated. The optical spectra of all samples exhibited two distinct regions of optical gap, E_op1 suggesting a direct allowed transition with optical gap ranging from 0.37 up to 0.42 eV and E_op2 suggesting a direct forbidden transition with optical gap ranging from 2.02 up to 2.23 eV. This indicates that K_xV₂O₅·nH₂O films have more than one type of conduction mechanism.     

La(ClO4)3-OCBAAP-H2O体系(30℃)溶度及Ln(OCBAAP)4(ClO4)3·nH2O的合成和表征

测定了三元体系Ｌａ（ＣｌＯ４）３－ＯＣＢＡＡＰ－Ｈ２Ｏ在３０℃时的溶解度．结果表明，该体系有一个新固相（不一致溶解化合物）Ｌａ（ＯＣＢＡＡＰ）４（ＣｌＯ４）３·６Ｈ２Ｏ形成．参考该体系溶度图确定合成条件，合成了系列化合物Ｌｎ（ＯＣＢＡＡＰ）４（ＣｌＯ４）３·ｎＨ２Ｏ（Ｌｎ＝Ｌａ，ｎ＝６；Ｌｎ＝Ｐｒ，Ｎｄ，Ｓｍ，Ｇｄ，Ｙｂ，ｎ＝２）．通过化学分析、元素分析、ＴＧ－ＤＴＧ、ＩＲ和密度对化合物进行了表征，计算了Ｌａ（ＯＣＢＡＡＰ）４（ＣｌＯ４）３热分解过程各阶段的表观活化能．     

Crystal Structure and Properties of Rb4H2I2O10 · 4H2O

Single crystals of the Rb₄H₂I₂O₁₀· 4H₂O were synthesized for the first time and studied by X-ray diffraction analysis. The crystals are monoclinic, a = 7.321(6) Å, b = 12.599(8) Å, c = 8.198(8) Å, = 96.30(7)°, Z = 2, space group P2₁/c. The H₂I₂O₁₀ ^4– anion is formed by the edge-sharing IO₆ octahedra. The anions are united by hydrogen bonds into a chain running along the x axis. The chains are combined by water molecules into a three-dimensional structure through hydrogen bonds. The compound is a proton conductor. The conductivity values measured at 20–60°C vary within 10^–6 to 10^–4 ohm^–1 cm^–1.