Synthesis and structural characterization of 0D vanadium borophosphate [Co(en)(3)](2)[V(3)P(3)BO(19)][H(2)PO(4)].4H(2)O and 1D vanadium oxides [Co(en)(3)][V(3)O(9)].H(2)O and [Co(dien)(2)][V(3)O(9)].H(2)O templated by cobalt complexes: cooperative organization of the complexes and the inorganic networks

A 0D vanadium borophosphate [Co(en)(3)](2)[V(3)P(3)BO(19)][H(2)PO(4)].4H(2)O (1) and two 1D vanadium oxides [Co(en)(3)][V(3)O(9)].H(2)O (2) and [Co(dien)(2)][V(3)O(9)].H(2)O (3) have been synthesized hydrothermally from the reaction mixture of V(2)O(5)-H(3)PO(4)-H(3)BO(3)-CoCl(2)-R-H(2)O at 110 degrees C (R: en or dien). The complex cations Co(en)(3)(3+) and Co(dien)(2)(3+) are cooperatively organized in the reaction medium to play a structure-directing role in the formation of the inorganic clusters and chains. The structures are determined by single-crystal X-ray diffraction analysis and further characterized by X-ray powder diffraction, ICP, and TG analyses. The structure of 1 contains isolated [V(3)P(3)BO(19)](5)(-) cluster anions, H(2)PO(4)(-) anions, racemic Co(en)(3)(3+) cations, and H(2)O molecules, which form a complex H-bond network. 2 and 3 both contain chains of corner-sharing VO(4) tetrahedra running along the 2(1) screw axis. The complex cations located in the interchain region interact with the chains through H-bonds. 2 is crystallized in an enantiomorphic space group and only one enantiomer of Co(en)(3)(3+) is involved in the structure. Crystal data: 1, monoclinic, C2/c, a = 32.8492(14) A, b = 11.9601(3) A, c = 22.6001(7) A, beta = 108.9630(8) degrees, Z = 8; 2, orthorhombic, P2(1)2(1)2(1), a = 8.1587(16) A, b = 12.675(3) A, c = 18.046(4) A, Z = 4; 3, monoclinic, P2(1)/c, a = 16.1663(10) A, b = 8.7028(3) A, c = 13.9773(5) A, beta = 103.1340(18) degrees, Z = 4.     

NH4]2Mn3(H2O)4[Mo(CN)7]2.4H2O: tuning dimensionality and ferrimagnetic ordering temperature by cation substitution

[NH(4)](2)Mn(3)(H(2)O)(4)[Mo(CN)(7)](2).4H(2)O (1) has been synthesized by slow diffusion of aqueous solutions containing K(4)[Mo(CN)(7)].2H(2)O, [Mn(H(2)O)(6)](NO(3))(2), and (NH(4))NO(3). Compound 1 crystallizes in the monoclinic C2/c space group. The basic motif of the three-dimensional structure consists of a Mo1-Mn1 gridlike sheet parallel to the bc plane. Two of these sheets are connected through CN-Mn2-NC linkages to form a bilayer reminiscent of the K(2)Mn(3)(H(2)O)(6)[Mo(CN)(7)](2).6H(2)O (2) two-dimensional structure. In 1, [NH(4)](+) cations allow these bilayers to be connected through direct Mo1-CN-Mn1 bridges to form a three-dimensional network, whereas in 2, they are isolated by (H(2)O)K(+) cations. As shown by the magnetic measurements, this increase of dimensionality by counterion substitution induces an enhancement of the ferrimagnetic critical temperature from 39 K in 2 to 53 K in 1.     

新颖四核镍夹心的杂化锗钨酸盐的合成、结构与表征

在水热条件下合成了一个新颖的夹心结构四核镍有机-无机杂化锗钨酸盐[Ni(dien)(H2O)3]2·[Ni(Hdien)2]{[Ni(dien)]2Ni4(H2O)2(GeW9O34)2}·10H2O(1), 利用X射线单晶衍射确定了其结构, 并通过红外光谱、热重、X射线粉末衍射、X射线能谱和元素分析对其进行了表征. 其晶体属三斜晶系, P1, a=1.1937(3) nm, b=1.4323(3) nm, c=1.6394(4) nm, α=93.424(2)°, β=96.058(3)°, γ=109.758(4)°, V=2.6094(1) nm3,Z=1. X射线单晶衍射结果表明, 化合物1是由夹心构型的多阴离子通过镍-二乙烯三胺配阳离子连接形成的一维线性结构.     

Anion-directed crystallization of coordination polymers: syntheses and characterization of Cu(4)(2-pzc)(4)(H(2)O)(8)(Mo(8)O(26)).2H(2)O and Cu(3)(2-pzc)(4)(H(2)O)(2)(V(10)O(28)H(4)).6.5H(2)O (2-pzc = 2-pyrazinecarboxylate)

Two new copper 2-pyrazinecarboxylate (2-pzc) coordination polymers incorporating [Mo(8)O(26)](4-) and [V(10)O(28)H(4)](2-) anions were synthesized and structurally characterized: Cu(4)(2-pzc)(4))(H(2)O)(8)(Mo(8)O(26)).2H(2)O (1) and Cu(3)(2-pzc)(4)(H(2)O)(2)(V(10)O(28)H(4)).6.5H(2)O (2). Crystal data: 1, monoclinic, space group P2(1)/n, a = 11.1547(5) A, b = 13.4149(6) A, c = 15.9633(7) A, beta = 90.816(1) degrees; 2, triclinic, space group P1, a = 10.5896(10) A, b = 10.7921(10) A, c = 13.5168(13) A, alpha = 104.689(2) degrees, beta = 99.103(2) degrees, gamma = 113.419(2) degrees. Compound 1 contains [Cu(2-pzc)(H(2)O)(2)] chains charge-balanced by [Mo(8)O(26)](4-) anions. In compound 2, layers of [Cu(3)(2-pzc)(4)(H(2)O)(2)] form cavities that are filled with [V(10)O(28)H(4)](2-) anions. The magnetic properties of both compounds are described.     

Organically templated uranium(IV) fluorooxalates with layer structures: (H4TREN)[U2F6(C2O4)3].4H2O (TREN = tris(2-aminoethyl)amine) and (H4APPIP)[U2F6(C2O4)3].4H2O (APPIP = 1,4-bis(3-amino-propyl)piperazine)

Two organically-templated layered uranium(IV) fluorooxalates, (H(4)TREN)[U(2)F(6)(C(2)O(4))(3)].4H(2)O (1) (TREN = tris(2-aminoethyl)amine) and (H(4)APPIP)[U(2)F(6)(C(2)O(4))(3)].4H(2)O (2) (APPIP = 1,4-bis(3-aminopropyl)piperazine), have been synthesized by hydrothermal methods and structurally characterized by single-crystal X-ray diffraction, thermogravimetric analysis, and magnetic susceptibility. Both structures consist of anionic [U(2)F(6)(C(2)O(4))(3)](4-) layers separated by organic ammonium cations and lattice water molecules. The UF(3)O(6) polyhedra are connected by oxalate ligands in different ways within the layers. They are the first examples of organically-templated uranium fluorooxalates. Crystal data for compound 1 follow: monoclinic, P2(1)/c (No. 14), a = 19.1563(5) A, b = 8.9531(2) A, c = 16.6221(4) A, beta = 114.633(1) degrees, and Z = 4. Crystal data for compound are the same as those for 1 except a = 10.3309(8) A, b = 15.564(1) A, c = 17.537(1) A, and beta = 95.430(4) degrees.     

Cation-cation interactions: crystal structures of neptunyl(V) selenate hydrates, (NpO2)2(SeO4)(H2O)n (n=1, 2, and 4)

Green crystals of (NpO(2))(2)(SeO(4))(H(2)O)(4), (NpO(2))(2)(SeO(4))(H(2)O)(2), and (NpO(2))(2)(SeO(4))(H(2)O) have been prepared by hydrothermal methods. The structures of these compounds have been characterized by single-crystal X-ray diffraction. (NpO(2))(2)(SeO(4))(H(2)O)(4), isostructural with (NpO(2))(2)(SO(4))(H(2)O)(4), is constructed from layers comprised of corner-sharing neptunyl(V) pentagonal bipyramids and selenate tetrahedra that are further linked by hydrogen bonding with water molecules. Each NpO(2)(+) cation binds to four other NpO(2)(+) units through cation-cation interactions (CCIs) to form a distorted "cationic square net" decorated by SeO(4)(2-) tetrahedra above and below the layer. Each selenate anion is bound to two neptunyl(V) cations through monodentate linkages. (NpO(2))(2)(SeO(4))(H(2)O)(2) is isostructural with the corresponding sulfate analogue as well. It consists of puckered layers of neptunyl(V) pentagonal bipyramids that are further connected by selenate tetrahedra to form a three-dimensional framework. The CCI pattern in the neptunyl layers of dihydrate is very similar to that of tetrahydrate; however, each SeO(4)(2-) tetrahedron is bound to four NpO(2)(+) cations in a mondentate manner. (NpO(2))(2)(SeO(4))(H(2)O) crystallizes in the monoclinic space group P2(1)/c, which differs from the (NpO(2))(2)(SO(4))(H(2)O) orthorhombic structure due to the slightly different connectivities between NpO(2)(+) cations and anionic ligands. The structure of (NpO(2))(2)(SeO(4))(H(2)O) adopts a three-dimensional network of distort neptunyl(V) pentagonal bipyramids decorated by selenate tetrahedra. Each NpO(2)(+) cation connects to four other NpO(2)(+) units through CCIs and also shares an equatorial coordinating oxygen atom with one of the other units in addition to the CC bond to form a dimer. Each SeO(4)(2-) tetrahedron is bound to five NpO(2)(+) cations in a monodentate manner. Magnetic measurements obtained from the powdered tetrahydrate are consistent with a ferromagnetic ordering of the neptunyl(V) spins at 8(1) K, with an average low temperature saturation moment of 1.98(8) μ(B) per Np. Well above the ordering temperature, the susceptibility follows Curie-Weiss behavior, with an average effective moment of 3.4(2) μ(B) per Np and a Weiss constant of 14(4) K. Correlations between lattice dimensionality and magnetic behavior are discussed.     

The mechanism of proton exchange: guided ion beam studies of the reactions, H(H2O)n+ (n=1-4)+D2O and D(D2O)n+ (n=1-4)+H2O

Reactions of protonated water clusters, H(H(2)O)(n) (+) (n=1-4) with D(2)O and their "mirror" reactions, D(D(2)O)(n) (+) (n=1-4) with H(2)O, are studied using guided-ion beam mass spectrometry. Absolute reaction cross sections are determined as a function of collision energy from thermal energy to over 10 eV. At low collision energies, we observe reactions in which H(2)O and D(2)O molecules are interchanged and reactions where H-D exchange has occurred. As the collision energy is increased, the H-D exchange products decrease and the water exchange products become dominant. At high collision energies, processes in which one or more water molecules are lost from the reactant ions become important, with simple collision-induced dissociation processes, i.e., those without H-D exchange, being dominant. Threshold energies of endothermic channels are measured and used to determine binding energies of the proton bound complexes, which are consistent with those determined by thermal equilibrium measurements and previous collision-induced dissociation studies. A kinetic scheme that relies only on the ratio of isomerization and dissociation rate constants successfully accounts for the kinetic energy dependence observed in the branching ratios for H-D and water exchange products in all systems. Rice-Ramsperger-Kassel-Marcus theory and ab initio calculations confirm the feasibility and establish the details of this kinetic model.     

Isotope exchange in reactions between D2O and size-selected ionic water clusters containing pyridine, H+ (pyridine)m(H2O)n

Pyridine containing water clusters, H(+)(pyridine)(m)(H(2)O)(n), have been studied both experimentally by a quadrupole time-of-flight mass spectrometer and by quantum chemical calculations. In the experiments, H(+)(pyridine)(m)(H(2)O)(n) with m = 1-4 and n = 0-80 are observed. For the cluster distributions observed, there are no magic numbers, neither in the abundance spectra, nor in the evaporation spectra from size selected clusters. Experiments with size-selected clusters H(+)(pyridine)(m)(H(2)O)(n), with m = 0-3, reacting with D(2)O at a center-of-mass energy of 0.1 eV were also performed. The cross-sections for H/D isotope exchange depend mainly on the number of water molecules in the cluster and not on the number of pyridine molecules. Clusters having only one pyridine molecule undergo D(2)O/H(2)O ligand exchange, while H(+)(pyridine)(m)(H(2)O)(n), with m = 2, 3, exhibit significant H/D scrambling. These results are rationalized by quantum chemical calculations (B3LYP and MP2) for H(+)(pyridine)(1)(H(2)O)(n) and H(+)(pyridine)(2)(H(2)O)(n), with n = 1-6. In clusters containing one pyridine, the water molecules form an interconnected network of hydrogen bonds associated with the pyridinium ion via a single hydrogen bond. For clusters containing two pyridines, the two pyridine molecules are completely separated by the water molecules, with each pyridine being positioned diametrically opposite within the cluster. In agreement with experimental observations, these calculations suggest a "see-saw mechanism" for pendular proton transfer between the two pyridines in H(+)(pyridine)(2)(H(2)O)(n) clusters.     

A family of new glutarate compounds: synthesis, crystal structures of: Co(H2O)5L(1), Na2[CoL2] (2), Na2[L(H2L)4/2] (3), {[Co3(H2O)6L2](HL)2}.4H2O (4), {[Co3(H2O)6L2](HL)2}.10H2O (5), {[Co3(H2O)6L2]L2/2}.4H2O (6), and Na2{[Co3(H2O)2]L8/2].6H2O (7), and magnetic properties of 1 and 2 with H2L = HOOC-(CH2)3-COOH

Seven new glutaric acid complexes, Co(H 2O) 5L 1, Na 2[CoL 2] 2, Na 2[L(H 2L) 4/2] 3, {[Co 3(H 2O) 6L 2](HL) 2}.4H 2O 4, {[Co 3(H 2O) 6L 2](HL) 2}.10H 2O 5, {[Co 3(H 2O) 6L 2]L 2/2}.4H 2O 6, and Na 2{[Co 3(H 2O) 2]L 8/2].6H 2O 7 were obtained and characterized by single-crystal X-ray diffraction methods along with elemental analyses, IR spectroscopic and magnetic measurements (for 1 and 2). The [Co(H 2O) 5L] complex molecules in 1 are assembled into a three-dimensional supramolecular architecture based on intermolecular hydrogen bonds. Compound 2 consists of the Na (+) cations and the necklace-like glutarato doubly bridged [ C o L 4 / 2 ] 2 - infinity 1 anionic chains, and 3 is composed of the Na (+) cations and the anionic hydrogen bonded ladder-like [ L ( H 2 L ) 4 / 2 ] 2 - infinity 1 anionic chains. The trinuclear {[Co 3(H 2O) 6L 2](HL) 2} complex molecules with edge-shared linear trioctahedral [Co 3(H 2O) 6L 2] (2+) cluster cores in 4 and 5 are hydrogen bonded into two-dimensional (2D) networks. The edge-shared linear trioctahedral [Co 3(H 2O) 6L 2] (2+) cluster cores in 6 are bridged by glutarato ligands to generate one-dimensional (1D) chains, which are then assembled via interchain hydrogen bonds into 2D supramolecular networks. The corner-shared linear [Co 3O 16] trioctahedra in 7 are quaternate bridged by glutarato ligands to form 1D band-like anionic {[Co 3(H 2O) 2]L 8/2} (2+) chains, which are assembled via interchain hydrogen bonds into 2D layers, and between them are sandwiched the Na (+) cations. The magnetic behaviors of 1 and 2 obey the Curie-Weiss law with chi m = C/( T - Theta) with the Curie constant C = 3.012(8) cm (3) x mol (-1) x K and the Weiss constant Theta = -9.4(7) K for 1, as well as C = 2.40(1) cm (3) x mol (-1) x K and Theta = -2.10(5) K for 2, indicating weak antiferromagnetic interactions between the Co(II) ions.     

Cation-directed synthesis of tungstosilicates. 1. Syntheses and structures of K10A-alpha-[SiW9O34].24H2O,of the sandwich-type complex K10.75[Co(H2O)6]0.5[Co(H2O)4Cl]0.25A-alpha-[K2(Co(H2O)2)3(SiW9O34)2].32H2O and of Cs15[K(SiW11O39)2].39H2O

The influence of the nature of alkali metal cations on the structure of the species obtained from the trivacant precursor A-alpha-[SiW(9)O(34)](10-) has been studied. Starting from the potassium salt 1, K(10)A-alpha-[SiW(9)O(34)].24H(2)O, the sandwich-type complex 2, K(10.75)[Co(H(2)O)(6)](0.5)[Co(H(2)O)(4)Cl](0.25)A-alpha-[K(2)(Co(H(2)O)(2))(3)(SiW(9)O(34) )(2)].32H(2)O, has been obtained. The crystal structures of these two compounds consist of two A-alpha-[SiW(9)O(34)](10-) anions linked by a set of potassium (1) or cobalt plus potassium cations (2), and the relative orientation of the two half-anions is the same. Attempts to link two A-alpha-[SiW(9)O(34)](10-) anions by tungsten atoms instead of cobalt failed whatever the alkali metal cation. Moreover, the nondisordered structure of Cs(15)[K(SiW(11)O(39))(2)].39H(2)O is described. Two [SiW(11)O(39)](8-) anions are linked through a potassium cation with a "trans-oid" conformation, and the potassium occupies a cubic coordination site.     

Polynuclear complexes with bridging pyrophosphate ligands: synthesis and characterisation of {[(bipy)Cu(H2O)(mu-P2O7)Na2(H2O)6] x 4H2O}, {[(bipy)Zn-(H2O)(mu-P2O7)Zn(bipy)]2 x 14H2O} and {[(bipy)(VO)2]2(mu-P2O7)] x 5H2O}

The reaction in water of M(II) ions (M = Cu, 1; Zn, 2; VO, 3) with 2,2'-bipyridine (bipy) followed by Na4P2O7 leads to the formation of three new complexes which feature the pyrophosphate anion, P2O7(4-), as a bridging ligand. Single crystal X-ray diffraction revealed 1 to be {[(bipy)Cu(H2O)(micro-P2O7)Na2(H2O)6] x 4H2O}, and 2 as a tetranuclear Zn(II) complex, {[(bipy)Zn(H2O)(micro-P2O7)Zn(bipy)]2 x 14H2O}. The structure of 1 consists of a mononuclear [(bipy)Cu(H2O)(P2O7)]2- unit that links via a pyrophosphate bridge to two Na atoms. The hydrated six-coordinate Na atoms themselves join together through bridging water molecules to generate a 2D Na-water sheet. The structure of 2 consists of a tetranuclear Zn(II) cluster (dimer-of-dimers) with two pyrophosphate ligands bridging between four metal centres. Adjacent clusters interact through face-to-face pi-pi interactions via the bipy ligands to yield a 2D sheet. Adjacent sheets pack in register to create channels, which are filled by the water molecules of crystallisation. An intricate 2D H-bonded water network separates adjacent sheets and encapsulates the tetranuclear clusters. Aspects of the pyrophosphate coordination modes in 1 and 2 are of structural relevance to those found within the inorganic pyrophosphatases. Compound 3, {[(bipy)(VO)2]2(micro-P2O7)] x 5H2O}, was isolated as an insoluble lime-green powder. Its dinuclear structure was elucidated from elemental and thermal analysis, magnetic susceptibility measurement and IR spectroscopy. The latter displayed characteristic bridging pyrophosphate and signature V=O stretches, which were corroborated by contrast to the IR spectra of 1 and 2 and through comparison with those found in the structurally characterised dinuclear complex, {[(bipy)Cu(H2O)]2(micro-P2O7) x 7H2O}, 4.     

Observation of the pi...H hydrogen-bonded ternary complex, (C(2)H(4))(2)H(2)O, using matrix isolation infrared spectroscopy

FTIR absorption spectra of water-containing ethene:Ar matrices, with compositions of ethene up to 1:10 ethene:Ar, have been recorded. Systematically increasing the concentration of ethene reveals features in the spectra consistent with the known 1:1 ethene:water complex, which subsequently disappear on further increase in ethene concentration. At high concentrations of ethene, new features are observed at 3669 and 3585 cm(-1), which are red-shifted with respect to matrix-isolated nu(3) and nu(1) O-H stretching modes of water and the 1:1 ethene:water complex. These shifts are consistent with a pi...H interaction of a 2:1 ethene:water complex of the form (C(2)H(4)...H-O-H...C(2)H(4)). The analogous (C(2)D(4))(2)H(2)O complex shows little shifting from positions associated with (C(2)H(4))(2)H(2)O, while the (C(2)H(4))(2)D(2)O isotopomer shows large shifts to 2722.3 and 2617.2 cm(-1), having identical nu(3)(H(2)O)/nu(3)(D(2)O) and nu(1)(H(2)O)/nu(1)(D(2)O) values when compared with monomeric water isotopomers. Features at 3626.1 and 2666.2 cm(-1) are also observed and are attributed to (C(2)H(4))(2)HDO. DFT calculations at the B3LYP/6-311+G(d,p) level for each isotopomer are presented, and the predicted vibrational frequencies are directly compared with experimental values. The interaction energy for the formation of the 2:1 ethene:water complex from the 1:1 ethene:water complex is also presented.     

Synthesis and characterization of (R-C5H14N2)2[Ga4(C2O4)(H2PO4)2(PO4)4].2H2O, a layered gallium phosphatooxalate containing a chiral amine

The first metal phosphatooxalate containing a chiral amine, (R-C5H14N2)2[Ga4(C2O4)(H2PO4)2(PO4)4].2H2O, has been synthesized hydrothermally and characterized by single-crystal X-ray diffraction and 31P MAS NMR spectroscopy. It crystallizes in the monoclinic space group P2(1) (No. 4) with a = 8.0248(4) A, b = 25.955(1) A, c = 9.0127(5) A, beta = 100.151(1) degrees, and Z = 2. The structure consists of GaO6 octahedra and GaO4 tetrahedra connected by coordinating C2O4(2-) and phosphate anions to form anionic sheets in the ac plane with charge-compensating diprotonated R-2-methylpiperazinium cations and water molecules between the layers. There is a good correlation between the NMR spectrum and the structure.     

Crystal structure of [Al4(OH)6(H2O)12][Al(H2O)6]2Br12: a new polyaluminum compound

A vertex-shared tetrahedral [Al(4)(OH)(6)(H(2)O)(12)](6+) (Al(4)) and a disordered [Al(H(2)O)(6)](3+) (Al(1)) that coexist in a 1:2 ratio within each unit cell were observed in the structure of [Al(4)(OH)(6)(H(2)O)(12)][Al(H(2)O)(6)](2)Br(12), which crystallized in a cubic Fd3m space group from a spontaneously hydrolyzed solution of AlBr(3). The former is composed of four AlO(6) octahedra that are connected to each other by sharing three vertexes of each octahedron and form a large regular tetrahedron with ideal T(d) symmetry. The central Al(3+) ion of the latter is coordinated by 6 disordered OH(2) molecules, that form a core-shell structure with ideal D(3d) symmetry.     

A new organic-inorganic hybrid layered molybdenum(V) cobalt phosphate constructed from [H24(Mo16O32)Co16(PO4)24(OH)4(C5H4N)2(H2O)6](4-) wheels and 4,4'-bipyridine linkers

A new layered molybdenum cobalt phosphate, Na(2)[Co(H(2)O)(6)][(Mo(16)O(32))Co(16)(PO(4))(4) (HPO(4))(16)(H(2)PO(4))(4)(OH)(4)(C(10)H(8)N(2))(4)(C(5)H(4)N)(2)(H(2)O)(6)]·4H(2)O (1), has been hydrothermally synthesized and structurally characterized. 1 crystallizes in the monoclinic space group P2(1)/n with a = 15.6825(18) ?, b = 39.503(4) ?, c = 17.2763(17) ?, β = 93.791(2)°, V = 10679.4(18) ?(3), and Z = 2. A polyoxoanion of 1 exhibits an unusual organic-inorganic hybrid wheel-type cluster, in which two pyridine ligands link to the surface Co(II) atoms of a [H(24)(Mo(16)O(32))Co(16)(PO(4))(24)(OH)(4)(H(2)O)(6)] (namely, {Mo(16)Co(16)P(24)}) wheel via the Co-N bonds. Furthermore, each {Mo(16)Co(16)P(24)} wheel is connected to four adjacent wheels by four pairs of 4,4'-bipyridine linkers, forming a 2D layered network. The susceptibility measurement shows the existence of dominant antiferromagnetic interactions in 1.     

Synthesis, structural characterization and properties of a 3D infinitely extended structural rare earth coordination compound of K3{[Sm(H2O)7]2Na[α-SiW11O39Sm(H2O)4]2}·14 H2O

A 3D infinitely extended structural rare earth coordination compound with a formula of K3{[Sm(H2O)7]2Na[α-SiW11O39Sm(H2O)4]2}·14H2O has been synthesized by reaction of Sm2O3, HClO4, NaOH with α-K8SiW11O39·nH2O, and characterized by IR,UV spectra, ICP, TG-DTA, cyclic voltammetry, variable-temperature magnetic susceptibility and X-ray single-crystal diffraction.X-ray single-crystal diffraction indicates that the title compound crystallizes in a triclinic lattice, Pī space group, with a=1.2462(3) nm, b=1.2652(3) nm,c=1.8420(4) nm,α=87.45(3)°,β=79.91(3)°,γ=82.57(3)°,Z=1, R1=0.0778,wR2=0.1610.Structural analysis reveals that Sm3+(1) coordination cation has incorporated into the vacant site of [α-SiW11O39]8- entity,forming the [α-SiW11O39Sm(H2O)4]5- subunit.The two adjacent [α-SiW11O39Sm(H2O)4]5- subunits are combined with each other through two Sm(1)-O-W bridges accompanying the formation of dimmer structural unit [α-SiW11O39Sm(H2O)4]210- of the title compound.The neighboring dimmer structural units [α-SiW11O39Sm(H2O)4]210- are linked to form the 1D chainlike structure by means of two Sm3+(2) and a Na+(1) coordination cations.The K+(1) cations connect the 1D packing chains constructing the 2D netlike structure, and adjacent netlike layers are also grafted by K+(2) cations to build the novel 3D infinitely extended structure.The result of TG-DTA curves manifests that the decomposition temperature of the title polyanionic framework is 554℃.The cyclic voltammetry measurements show that the title polyanion has the two-step redox processes in aqueous solution with pH=3.1.Variable temperature magnetic susceptibility indicates the title compound obeys the Cruie-Weiss Law in the higher temperature range from 110 to 300 K, while in the lower temperature range from 2 to 110 K the comparatively strong antiferromagnetism interactions can be observed.     

Ni2O(L-Asp)(H2O)2)].4H2)O: a homochiral 1D helical chain hybrid compound with extended Ni-O-Ni bonding

The hydrothermally synthesized 1D homochiral nickel aspartate oxide [Ni2O(l-Asp)(H2O)2].4H2O is based on infinite helical chains of edge- and corner-sharing nickel octahedra. It represents the first example of a chiral one-dimensional compound with an extended helical TM-O-TM subnetwork synthesized as an optically pure product. Its structure was determined ab initio by real-space methods from laboratory powder diffraction data.     

Syntheses, structures, and ion-exchange properties of the three-dimensional framework uranyl gallium phosphates, Cs4[(UO2)2(GaOH)2(PO4)4].H2O and Cs[UO2Ga(PO4)2

The reaction of UO(2)(NO(3))(2).6H(2)O with Cs(2)CO(3) or CsCl, H(3)PO(4), and Ga(2)O(3) under mild hydrothermal conditions results in the formation of Cs(4)[(UO(2))(2)(GaOH)(2)(PO(4))(4)].H(2)O (UGaP-1) or Cs[UO(2)Ga(PO(4))(2)] (UGaP-2). The structure of UGaP-1 was solved from a twinned crystal revealing a three-dimensional framework structure consisting of one-dimensional (1)(infinity)[Ga(OH)(PO(4))(2)](4-) chains composed of corner-sharing GaO(6) octahedra and bridging PO(4) tetrahedra that extend along the c axis. The phosphate anions bind the UO(2)(2+) cations to form UO(7) pentagonal bipyramids. The UO(7) moieties edge-share to create dimers that link the gallium phosphate substructure into a three-dimensional (3)(infinity)[(UO(2))(2)(GaOH)(2)(PO(4))(4)](4-) anionic lattice that has intersecting channels running down the b and c axes. Cs(+) cations and water molecules occupy these channels. The structure of UGaP-2 is also three-dimensional and contains one-dimensional (1)(infinity)[Ga(PO(4))(2)](3-) gallium phosphate chains that extend down the a axis. These chains are formed from fused eight-membered rings of corner-sharing GaO(4) and PO(4) tetrahedra. The chains are in turn linked together into a three-dimensional (3)(infinity)[UO(2)Ga(PO(4))(2)](1-) framework by edge-sharing UO(7) dimers as occurs in UGaP-1. There are channels that run down the a and b axes through the framework. These channels contain the Cs(+) cations. Ion-exchange studies indicate that the Cs(+) cations in UGaP-1 and UGaP-2 can be exchanged for Ca(2+) and Ba(2+). Crystallographic data: UGaP-1, monoclinic, space group P2(1)/c, a = 18.872(1), b = 9.5105(7), c = 14.007(1) A, beta = 109.65(3)(o) , Z = 4 (T = 295 K); UGaP-2, triclinic, space group P, a = 7.7765(6), b = 8.5043(7), c = 8.9115(7) A, alpha = 66.642(1)(o), beta = 70.563(1)(o), gamma = 84.003(2)(o), Z = 2 (T = 193 K).     

NMR studies of heteropolyanion [P(2)W(20)O(70)(H2O)2](-10) complexes with metal cations

We have used multinuclear NMR and IR spectroscopy to study the interaction of a number of metal cations with monovacant heteropolyanion [P(2)W(20)O(7)(0)(H(2)O)(2)](10)(-) (P(2)W(20)) in aqueous solutions starting from its K salt. We have also prepared and studied P(2)W(20) in an Na-only medium. The observed differences in the NMR spectra of NaP(2)W(20)and KP(2)W(20)solutions and the importance of K(+) and Na(+) for the formation of P(2)W(20) suggest that this polyanion exists only as a complex with the alkaline cations. When both cations were simultaneously present in solution, we observed the broadening of the NMR signals of P(2)W(20)due to the Na-K exchange. Li(+) does not replace K(+) or Na(+) in such complexes, and in an Li-only medium P(2)W(20) does not form. Of all the M(n)(+) cations studied (Pd(2+), Bi(3+), Sn(4+), Zr(4+), Ce(4+), Ti(4+), V(5+), and Mo(6+)) only Bi(3+), Sn(4+), and Ce(4+) form complexes with P(2)W(20) in strongly acidic solutions. The (183)W and (119)Sn NMR data suggest that Sn(4+) forms in solution two mutually interconvertable P(2)W(20)Sn complexes of the composition P(2)W(20)O(70)(H(2)O)(3)SnOH(7)(-) and (P(2)W(20)O(70)(H(2)O)(3)Sn)(2)O(14)(-) while Bi(3+) forms one complex of the proposed composition P(2)W(20)O(70)(H(2)O)(2)Bi.(7)(-) We obtained complexes with Bi and Sn as free heteropoly acids and studied their thermostability in the solid state.     

A hydrothermal investigation of the 1/2V2O5-H2C2O4/H3PO4/NH4OH system: synthesis and structures of (NH4)VOPO(4).1.5H2O, (NH4)0.5VOPO(4).1.5H2O, (NH4)2[VO(H2O)3]2[VO(H2O)][VO(PO4)2](2).3H2O, and (NH4)2[VO(HPO4)]2(C2O4).5H2O

The 1/2V2O5-H2C2O4/H3PO4/NH4OH system was investigated using hydrothermal techniques. Four new phases, (NH4)VOPO(4).1.5H2O (1), (NH4)0.5VOPO(4).1.5H2O (2), (NH4)2[VO(H2O)3]2[VO(H2O)][VO(PO4)2]2.3H2O (3), and (NH4)2[VO(HPO4)]2(C2O4).H2O (4), have been prepared and structurally characterized. Compounds 1 and 2 have layered structures closely related to VOPO(4).2H2O and A0.5VOPO4.yH2O (A = mono- or divalent metals), whereas 3 has a 3D open-framework structure. Compound 4 has a layered structure and contains both oxalate and phosphate anions coordinated to vanadium cations. Crystal data: (NH4)VOPO(4).1.5H2O, tetragonal (I), space group I4/mmm (No. 139), a = 6.3160(5) A, c = 13.540(2) A, Z = 4; (NH4)0.5VOPO(4).1.5H2O, monoclinic, space group P2(1)/m (No. 11), a = 6.9669(6) A, b = 17.663(2) A, c = 8.9304(8) A, beta = 105.347(1) degrees, Z = 8; (NH4)2[VO(H2O)3]2[VO(H2O)][VO(PO4)2]2.3H2O, triclinic, space group P1 (No. 2), a = 10.2523(9) A, b = 12.263(1) A, c = 12.362(1) A, alpha = 69.041(2) degrees, beta = 65.653(2) degrees, gamma = 87.789(2) degrees, Z = 2; (NH4)2[VO(HPO4)]2(C2O4).5H2O, monoclinic (C), space group C2/m (No. 12), a = 17.735(2) A, b = 6.4180(6) A, c = 22.839(2) A, beta = 102.017(2) degrees, Z = 6.