SYNTHESIS AND ~（183）W NMR CHARACTERIZATION OF P_4W_（30）Al_4（H_2O）_2O_（112）~（20－） HETEROPOLYANION

ＳＹＮＴＨＥＳＩＳ　ＡＮＤ　~（１８３）Ｗ　ＮＭＲ　ＣＨＡＲＡＣＴＥＲＩＺＡＴＩＯＮ　ＯＦ　Ｐ_４Ｗ_（３０）Ａｌ_４（Ｈ_２Ｏ）_２Ｏ_（１１２）~（２０－）　ＨＥＴＥＲＯＰＯＬＹＡＮＩＯＮＳＹＮＴＨＥＳＩＳＡＮＤ~（１８３）ＷＮＭＲＣＨＡＲＡＣＴＥＲＩＺ?..     

EFFECT OF WATER ON PERFORMANCE OF SILICALITE-2 ZEOLITE SUPPORTED Cr CATALYST FOR C_2H_4 PRODUCTION FROM C_2H_6 DEHYDROGENATION WITH CO_2

ＥＦＦＥＣＴＯＦＷＡＴＥＲＯＮＰＥＲＦＯＲＭＡＮＣＥＯＦＳＩＬＩＣＡＬＩＴＥ２ＺＥＯＬＩＴＥＳＵＰＰＯＲＴＥＤＣｒＣＡＴＡＬＹＳＴＦＯＲＣ２Ｈ４ＰＲＯＤＵＣＴＩＯＮＦＲＯＭＣ２Ｈ６ＤＥＨＹＤＲＯＧＥＮＡＴＩＯＮＷＩＴＨＣＯ２ＸｕＬｏｎｇｙａ，Ｗａｎ...     

SYNTHESIS AND STRUCTURE OF A 2D SHEET－LIKE COPPER（II） COMPLEX WITH BRIDGING PYRIDINE－4－CARBOXYLATE AND TRANS－OXAMIDATE LIGANDS

ＳＹＮＴＨＥＳＩＳＡＮＤＳＴＲＵＣＴＵＲＥＯＦＡ２ＤＳＨＥＥＴ－ＬＩＫＥＣＯＰＰＥＲ（ＩＩ）ＣＯＭＰＬＥＸＷＩＴＨＢＲＩＤＧＩＮＧＰＹＲＩＤＩＮＥ－４－ＣＡＲＢＯＸＹＬＡＴＥＡＮＤＴＲＡＮＳ－ＯＸＡＭＩＤＡＴＥＬＩＧＡＮＤＳ￥ＭｅｉＦａｎｇＷｕ；Ｚｈ...     

SYNTHESIS OF TETRAMETHYLDISILANDIYL DICYCLOPENTADIENYL LANTHANIDE COMPLEXES AND STRUCTURE OF 〔Me_4Si_2（C_5H_4）_2Sm（μ－Cl）（THF）〕_2

ＳＹＮＴＨＥＳＩＳＯＦＴＥＴＲＡＭＥＴＨＹＬＤＩＳＩＬＡＮＤＩＹＬＤＩＣＹＣＬＯＰＥＮＴＡＤＩＥＮＹＬＬＡＮＴＨＡＮＩＤＥＣＯＭＰＬＥＸＥＳＡＮＤＳＴＲＵＣＴＵＲＥＯＦ〔Ｍｅ_４Ｓｉ_２（Ｃ_５Ｈ_４）_２Ｓｍ（μ－Ｃｌ）（ＴＨＦ）〕_２￥ＦｕＱｕａｎＳＯ...     

非对称Schiff碱过渡金属配合物模拟酶催化烯烃环氧化（I）

研究了温和条件下以亚碘酰苯为氧源，非对称性的和对称性的Ｍｎ（Ⅲ）Ｓｃｈｉｆｆ碱配合物「Ｍｎ（Ⅲ）（ＣＢＰ－ｐｈｅｎ－Ｘｓａｌ）Ｃｌ，Ｘ＝Ｈ，Ｃｌ，Ｂｒ，Ｎｏ２，Ｃｈ３，ＯＣＨ３」和「Ｍｎ（Ⅲ）（ＣＢＰ－Ｒ－ＣＢＰ）Ｙ，Ｒ＝ＣＨ２ＣＨ２－，－ＣＨ（ＣＨ３）ＣＨ２－，－Ｃ６Ｈ４－；Ｙ＝Ｃｌ，ＯＣＨ３」催化非官能性烯烃苯乙烯，环己烯和α甲基苯乙烯的环氧化反应，结果表明，非对称配合物Ｍｎ（Ⅲ）的电子结合能     

ELECTROCHEMICAL BEHAVIOR OF MOLYBDOTUNGSATE HETEROPOLY COMPLEX WITH NEODYMIUMK_（10）H_3［Nd（SiMO_7W_4O_（39）_2）］xH_20 IN AQUEOUS SOLUTION

ＥＬＥＣＴＲＯＣＨＥＭＩＣＡＬＢＥＨＡＶＩＯＲＯＦＭＯＬＹＢＤＯＴＵＮＧＳＡＴＥＨＥＴＥＲＯＰＯＬＹＣＯＭＰＬＥＸＷＩＴＨＮＥＯＤＹＭＩＵＭＫ_（１０）Ｈ_３［Ｎｄ（ＳｉＭＯ_７Ｗ_４Ｏ_（３９）_２）］ｘＨ_２０ＩＮＡＱＵＥＯＵＳＳＯＬＵＴＩＯＮＸｉｕＭ?..     

STUDIES ON THE SOLID STATE REACTIONS OF COORDINATION COMPOUNDS： LXIX STEPWISE REACTION OF CuCl_2．2H_2O WITH 2，2＇－BIPYRIDYL

ＳＴＵＤＩＥＳＯＮＴＨＥＳＯＬＩＤＳＴＡＴＥＲＥＡＣＴＩＯＮＳＯＦＣＯＯＲＤＩＮＡＴＩＯＮＣＯＭＰＯＵＮＤＳ：ＬＸＩＸＳＴＥＰＷＩＳＥＲＥＡＣＴＩＯＮＯＦＣｕＣｌ_２．２Ｈ_２ＯＷＩＴＨ２，２＇－ＢＩＰＹＲＩＤＹＬ￥ＬｉＸｕＬＥＩａｎｄＸｉｎＱｕａｎＸ...     

SYNTHESIS AND CHARACTERIZATION OF HETEROBIMETALLIC COMPLEXES： （Cp_2LnOCH_2C_6H_5）Cr（CO）_3（Ln＝Gd，Dy，Yb，Y）

ＳＹＮＴＨＥＳＩＳ ＡＮＤ ＣＨＡＲＡＣＴＥＲＩＺＡＴＩＯＮ ＯＦ ＨＥＴＥＲＯＢＩＭＥＴＡＬＬＩＣ ＣＯＭＰＬＥＸＥＳ：（Ｃｐ_２ＬｎＯＣＨ_２Ｃ_６Ｈ_５）Ｃｒ（ＣＯ）_３（Ｌｎ＝Ｇｄ，Ｄｙ，Ｙｂ，Ｙ）￥ＣｈａｎｇＴａｏＱｉＡＮ；ＪｉａｎＨｕａＧＵＯ?..     

CRYSTAL STRUCTURE OF （Et_4N）_2Pd（i－MNT）_2 AND ITS REACTION WITH （Et_4N）_2WS_4 （i－MNT＝S_2CC（CN）_2~2－）

ＣＲＹＳＴＡＬＳＴＲＵＣＴＵＲＥＯＦ（Ｅｔ_４Ｎ）_２Ｐｄ（ｉ－ＭＮＴ）_２ＡＮＤＩＴＳＲＥＡＣＴＩＯＮＷＩＴＨ（Ｅｔ_４Ｎ）_２ＷＳ_４（ｉ－ＭＮＴ＝Ｓ_２ＣＣ（ＣＮ）_２~２－）￥ＤｅＬｉａｎｇＬＯＮＧ；ＸｉｎＱｕａｎＸＩＮ（ＳｔａｔｅＫｅｙＬａｂｏｒａ?..     

双金属杂原子分子筛CrCoBEA的合成、波谱及催化性能研究

采用水热晶化法首次合成出ＢＥＡ结构含铬、钴，双金属杂原子分子筛ＣｒＣｏＢＥＡ，对晶化时间，晶化温度，成胶配比等合成条件进行了优化研究，采用ＸＲＤ，ＦＴＩＲ，ＵＶ－ＶｉｓＤＲＳ，ＥＳＲ及催化反应等方法测试其物相、波谱性质和催化性能，结果表明物质的量比为ＴＥＯＳ：０．０１７「Ｃｒ（ａｃａｃ）３」：０．０１７「Ｃｏ（ａｃａｃ）３」：（０．５８－０．６４）ＴＥＡＯＨ：０．０１Ａｌ（ＮＯ３）３：（１６－２０     

Synthesis, crystal structure, and solid-state NMR spectroscopy of a new open-framework aluminophosphate (NH(4))(2)Al(4)(PO(4))(4)(HPO(4))xH(2)O

A new three-dimensional open-framework aluminophosphate (NH(4))(2)Al(4)(PO(4))(4)(HPO(4)).H(2)O (denoted AlPO-CJ19) with an Al/P ratio of 4/5 has been synthesized, using pyridine as the solvent and 2-aminopyridine as the structure-directing agent, under solvothermal conditions. The structure was determined by single-crystal X-ray diffraction and further characterized by solid-state NMR techniques. The alternation of the Al-centered polyhedra (including AlO(4), AlO(5), and AlO(6)) and the P-centered tetrahedra (including PO(4) and PO(3)OH) results in an interrupted open-framework structure with an eight-membered ring channel along the [100] direction. This is the first aluminophosphate containing three kinds of Al coordinations (AlO(4), AlO(5), and AlO(6)) with all oxygen vertexes connected to framework P atoms. (27)Al MAS NMR, (31)P MAS NMR, and (1)H --> (31)P CPMAS NMR characterizations show that the solid-state NMR techniques are an effective complement to XRD analysis for structure elucidation. Furthermore, all of the possible coordinations of Al and P in the aluminophosphates with an Al/P ratio of 4/5 are summarized. Crystal data: (NH(4))(2)Al(4)(PO(4))(4)(HPO(4))xH(2)O, monoclinic P2(1) (No. 4), a = 5.0568(3) A, b = 21.6211(18) A, c = 8.1724(4) A, beta = 91.361(4) degrees , V = 893.27(10) A(3), Z = 2, R(1) = 0.0456 (I > 2 sigma(I)), and wR(2) = 0.1051 (all data).     

An Alcohol-templated Borate Based on [B14O20（OH）6]4- Polyborate Anions

A new borate [H2EG][B7O10（OH）3] （1） based on [B14O20（OH）6]4- polyborate anions has been solvothermally synthesized in the presence of H2EG as a template （EG = ethylene glycol）. The structure was determined by single-crystal X-ray diffraction and further characterized by FFIR, elemental analysis and thermogravimetric analysis. Compound 1 crystallizes in the triclinic system, space group Pi, with a = 8.5095（4）, b = 8.8694（4）, c = 10.0756（4） A, a = 95.094（2）, β = 96.936（2）, γ = 116.844（2）°, V = 664.66（5） A3. The structure of 1 consists of [B14O20（OH）6]4- moiety, which could be regarded as the largest isolated polyborate anion so far. The anions are interlinked via hydrogen bonding to form a 3D supramolecular network, whereas the diprotonated [H2EG]2＋ are filled in the free space of inorganic borate network and interact with the inorganic framework by extensive hydrogen bonds. It is noteworthy that the EG acts not only as a solvent, but also as a template.     

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.     

(Fe(III)(OH(2))(2))(3)(A-alpha-PW(9)O(34))(2)](9-) on cationic silica nanoparticles,a new type of material and efficient heterogeneous catalyst for aerobic oxidations

Polyoxometalates (POMs) electrostatically bind to silica nanoparticles coated with cationic aluminum oxide "(Si/AlO2)n+" to form a new type of material (the anionic POMs replace Cl- counterions associated with the cationic surface sites). Association of a new approximately D3h POM of formula [(FeIII(OH2)2)3(A-alpha-PW9O34)2]9- (1) with the cationic nanoparticles (to form "K81/(Si/AlO2)") was studied in detail. Elemental analysis, particle sizes from both laser light scattering and TEM before and after association of 1, the size of 1 from X-ray crystallography, and other methods provide mutually consistent data that indicate about 58 K8[(FeIII(OH2)2)3(A-alpha-PW9O34)2]- monoanions associate with the average nanoparticle (diameter of the K81/(Si/AlO2) product = approximately 17 nm). While heterogeneity of the cationic sites and roughness of the (Si/AlO2)n+ surfaces make the associated POMs structurally nonuniform, the equivalent of approximately 1 monolayer of 1 is present in K81/(Si/AlO2). Remarkably, while 1, the precursor (Si/AlO2)n+, and the components of 1, each alone, are inactive as catalysts for O2/air-based oxidation of sulfides or aldehydes in solution, K81/(Si/AlO2) is an active catalyst for both reactions (facile reaction with air at low temperature).     

MIL-96, a porous aluminum trimesate 3D structure constructed from a hexagonal network of 18-membered rings and mu3-oxo-centered trinuclear units

A new aluminum trimesate Al12O(OH)18(H2O)3(Al2(OH)4)[btc]6.24H2O, denominated MIL-96, was synthesized under mild hydrothermal conditions (210 degrees C, 24 h) in the presence of 1,3,5-benzenetricarboxylic acid (trimesic acid or H3btc) in water. Hexagonal crystals, allowing a single-crystal XRD analysis, are grown from a mixture of trimethyl 1,3,5-benzenetricarboxylate (Me3btc), HF, and TEOS. The MIL-96 structure exhibits a three-dimensional (3D) framework containing isolated trinuclear mu3-oxo-bridged aluminum clusters and infinite chains of AlO4(OH)2 and AlO2(OH)4 octahedra forming a honeycomb lattice based on 18-membered rings. The two types of aluminum groups are connected to each other through the trimesate species, which induce corrugated chains of aluminum octahedra, linked via mu2-hydroxo bonds with the specific -cis-cis-trans- sequence. The 3D framework of MIL-96 reveals three types of cages. Two of them, centered at the special positions 0 0 0 and 2/3 1/3 1/4, have estimated pore volumes of 417 and 635 A3, respectively, and encapsulate free water molecules. The third one has a smaller pore volume and contains disordered aluminum octahedral species (Al(OH)6). The solid-state NMR characterization is consistent with crystal structure and elemental and thermal analyses. The four aluminum crystallographic sites are resolved by means of 27Al 3QMAS technique. This product is able to sorb both carbon dioxide and methane at room temperature (4.4 mmol.g(-1) for CO2 and 1.95 mmol.g(-1) for CH4 at 10 bar) and hydrogen at 77 K (1.91 wt % under 3 bar).     

Homogeneous forced hydrolysis of aluminum through the thermal decomposition of urea

Homogeneous hydrolysis of aluminum by decomposition of urea in solution was achieved because the urea coordinates to the Al3+ in solution, forming [Al(H2O)5 (urea)]3+ and to a lesser extent [Al(H2O)4 (urea)2]3+. Upon hydrolysis more hydrolyzed monomeric species, [Al(H2O)5 (OH)]2+, [Al(H2O)4 (OH)2]+, [Al(H2O)4 (urea)(OH)]2+, and [Al(H2O)3 (urea)(OH)2]+, were formed, followed by trimeric species and the Al13 Keggin complex [AlO4Al12(OH)24(H2O)12]7+. The 27Al NMR spectra indicated the formation of other complexes in addition to the Al13 at the end of the hydrolysis reaction.     

QD-2: a novel open-framework aluminoborate with intersecting three-dimensional helical channels

A novel open-framework aluminoborate, [CH3NH2(CH2)3NH ]-[AlB5O10] (QD-2), has been synthesized under hydrothermal conditions and characterized by IR, elemental analysis, thermogravimetric analysis, and powder and single-crystal X-ray diffractions. The compound crystallizes in the orthorhombic system, space group P2(1)2(1)2(1) (No. 19), a = 9.4352(4) A, b = 10.2972(2) A, c = 13.7511(5) A, V = 1336.0(8) A3, and Z = 4. Its structure consists of AlO4 tetrahedra and B5O10 clusters, which are interconnected to form the first example of a three-dimensional aluminoborate with intersecting helical channels.     

Heterometallic MIIRuIII2 compounds constructed from trans-[Ru(Salen)(CN)2]- and trans-[Ru(Acac)2(CN)2]-. Synthesis, structures, magnetic properties, and density functional theoretical study

The synthesis, structures, and magnetic properties of four cyano-bridged M(II)Ru(III)2 compounds prepared from the paramagnetic Ru(III) building blocks, trans-[Ru(salen)(CN)2]- 1 [H2salen = N,N'-ethylenebis(salicylideneimine)] and trans-[Ru(acac)2(CN)2]- (Hacac = acetylacetone), are described. Compound 2, {Mn(CH3OH)4[Ru(salen)(CN)2]2}.6CH3OH.2H2O, is a trinuclear complex that exhibits antiferromagnetic coupling between Mn(II) and Ru(III) centers. Compound 3, {Mn(H2O)2[Ru(salen)(CN)2]2.H2O}n, has a 2-D sheetlike structure that exhibits antiferromagnetic coupling between Mn and Ru, leading to ferrimagnetic-like behavior. Compound 4, {Ni(cyclam)[Ru(acac)2(CN)2]2}.2CH3OH.2H2O (cyclam = 1,4,8,11-tetraazacyclotetradecane), is a trinuclear complex that exhibits ferromagnetic coupling. Compound 5, {Co[Ru(acac)2(CN)2]2}n, has a 3-D diamond-like interpenetrating network that exhibits ferromagnetic ordering below 4.6 K. The density functional theory (DFT) method was used to calculate the molecular magnetic orbitals and the magnetic exchange interaction between Ru(III) and M(II) (Mn(II), Ni(II)) ions.     

CsSc[B2P3O11(OH)3]: a new borophosphate oligomer containing boron in three- and fourfold coordination

CsSc[B2P3O11(OH)3] was obtained by hydrothermal synthesis and represents the first alkali-metal scandium borophosphate containing boron with coordination numbers 3 and 4. The crystal structure was determined from single-crystal X-ray data: orthorhombic, space group Pnna (No. 52), a=13.0529(15) A, b=18.3403(17) A, c=10.3838(12) A, Z=8. The crystal structure contains the oligomeric unit [B2P3O11(OH)3]4- in which a central borate tetrahedron is open-branched by two (OH)PO3 tetrahedra and cyclobranched by one PO4 tetrahedron and a trigonal-planar (OH)BO2 by sharing common apexes. The borophosphate oligomers together with the ScO6 octahedra are condensed to form layers. Simultaneous difference thermal analysis and thermogravimetry revealed the stepwise decomposition of the compound in the temperature range between 333 and 973 K. Partly dehydrated samples do not show any substantial rehydration behavior. The crystal structure of CsSc[B2P3O11(OH)3] is discussed in connection with structural motifs of related borates and borophosphates.     

Self-assembly of a series of extended architectures based on polyoxometalate clusters and silver coordination complexes

Three unusual compounds based on polyoxometalate building blocks, [(H2O)5Na2(C6NO2H4)(C6NO2H5)3Ag2][Ag2IMo6O24(H2O)4] x 6.25H2O (1), [(H2O)4Na2(C6NO2H5)6Ag3][IMo6O24] x 6H2O (2), and (C6NO2H6)2[(C6NO2H5)2Ag][Cr(OH)6Mo6O18] x 4H2O (3), have been synthesized and characterized by elemental analysis; IR, XPS, and ESR spectroscopy; TG analysis; and single-crystal X-ray diffraction. Compound 1 is constructed from the cationic two-dimensional (2D) coordination polymer sheets which are constituted of [(H2O)5Na2(C6NO2H4)(C6NO2H5)3Ag2]3+ and anionic [Ag2IMo6O24(H2O)4]3- chains as pillars, forming a three-dimensional (3D) supramolecular framework via weak Ag-O interactions. Compound 2 is composed of the well-defined [IMo6O24]5- building blocks, which are linked through trinuclear Ag-pyridine-3-carboxylic acid, [(C6NO2H5)6Ag3]3+, fragments into a one-dimensional (1D) hybrid chain; adjacent chains are further connected by sodium cations to yield a novel 2D network. Compound 3 has a 1D chainlike structure constructed from [Cr(OH)6Mo6O18]3- building blocks and Ag-pyridine-4-carboxylic acid coordination units. The crystal data for these compounds are the following: 1, triclinic, P1, a = 13.280(3) A, b = 13.641(3) A, c = 16.356(3) A, alpha = 89.68(3) degrees, beta = 88.31(3) degrees, gamma = 75.87(3) degrees, Z = 2; 2, triclinic, P1, a = 11.978(2) A, b = 12.008(2) A, c = 13.607(3) A, alpha = 116.14(3) degrees, beta = 108.85(3) degrees, gamma = 93.86(3) degrees, Z = 1; 3, triclinic, P1, a = 10.458(2) A, b = 10.644(2) A, c = 12.295(3) A, alpha = 97.40(3) degrees, beta = 112.38(3) degrees, gamma = 113.59(3) degrees, Z = 1.