J. W. Zhao

Novel octatungstate-supported tricarbonyl metal derivatives: {[H2W8O30][M(CO)3]2}8- (M = Mn(I) and Re(I)).

Three novel octatungstate-supported tricarbonyl metal derivatives have been synthesized and characterized, which represent the first examples of isopolyoxotungstates-supported carbonyl metal compounds.

Synthesis of Cyclic Carbonates from Carbon Dioxide and Epoxides Catalyzed by a Keggin‐Type Polyoxometalate‐Supported Rhenium Carbonyl Derivate in Ionic Liquid

A monovacant Keggin‐type polyoxometalate‐supported trirhenium carbonyl derivate [(CH3)4N]5H23[(PW11O39){Re(CO)3}3(μ3‐O)(μ2‐OH)]4⋅24 H2O was synthesized. It was used as a catalyst for the synthesis of cyclic carbonates from carbon dioxide and epoxides under mild reaction conditions with co‐catalyst pyrrolidinium bromide. The catalyst system was recycled 10 times with only a small decline in yield. The catalytic mechanism was hypothesized based on experimental results and the frontier orbitals computed by DFT calculations.

Octamolybdate-supported tricarbonyl metal derivatives: [{H2Mo8O30}{M(CO)3}2]8- (M = Mn(I) and Re(I)).

Two novel octamolybdate-based tricarbonyl metal derivatives have been successfully synthesized and characterized, which represent the first two examples of tricarbonyl metal groups attached to a new {Mo(8)O(30)} building block.

A nona-vacant Keggin-type tricarbonyl rhenium derivative {[PMo3O16][Re(CO)3]4}5− and its catalytic performance for CO2 cycloaddition reactions

A nona-vacant Keggin-type tricarbonyl rhenium derivative [(NH4)5]{[PMo3O16][Re(CO)3]4}·1.5H2O was obtained and characterized. Its frontier orbitals were computed by density functional theory (DFT) calculations. Furthermore, it could act as a Lewis acid catalyst and promote the conversion of CO2 to cyclic carbonate under mild reaction conditions with pyrrolidinium bromide as a co-catalyst.

A novel 2D phosphomolybdate hybrid [Cu(En)(EnH)]2[P2Mo5O23] · 3H2O constructed from strandberg-type polyoxometalate units and copper-organic cation bridges

A 2D Strandberg-type phosphomolybdate hybrid [Cu(En)(EnH)]2[P2Mo5O23] · 3H2O (I) (En = ethylenediamine) has been successfully synthesized under hydrothermal conditions and structurally characterized by elemental analyses, IR spectrum, UV spectrum and single-crystal X-ray diffraction. The molecular structural unit of I consists of one Strandberg-type [P2Mo5O23]6− subunit, two [Cu(En)(EnH)]3+ cations and three lattice water molecules. The most remarkable feature of I is that each molecular structural unit is connected with adjacent four same units by four [Cu(En)(EnH)]3+ bridges constructing the 2D organic-inorganic hybrid sheet structure with a 4-connected topology. As far as we know, such 2D hybrid sheet structure constructed from Strandberg-type phosphomolybdate units and copper-organic cation bridges is very rare.

Biological activity of Co(III) and Ni(II) complexes of pyridine-2-carbaldehyde N(4)-methylthiosemicarbazone: Synthesis, characterization, crystal structure of Co(III) complex of pyridine-2-carbaldehyde N(4)-methylthiosemicarbazone1

Transition metal complexes formulated as [Co(L)2]ClO4 (I) and [Ni(L)2] · H2O (II), where HL = pyridine-2-carbaldehyde N(4)-methylthiosemicarbazone, have been synthesized. Complex I was characterized by elemental analysis, IR, MS and single-crystal X-ray diffraction studies. In complex I, the ligand is N2S tridentate, coordinating to the metal center through pyridine nitrogen, imine nitrogen and sulfur atoms. Hydrogen bonds link the different components to stabilize the crystal structure. Preliminary in vitro screening indicated that the free ligand was active against various bacteria and fungi and all the tested compounds showed significant antitumor activity against K562 leukaemia cell line, and can therefore be candidates for further stages of screening in vitro and/or in vivo.

Synthesis, structure, and photoluminescence properties of a novel 3D 3d-4f heterometallic polymer: Pr4(H2O)9Cu3.5Cl0.5(Bpdc)6.5(OH)2 · 5H2O (H2Bpdc = 2,2′-bipyridyl-5,5-dicarboxylic acid)

A novel 3D 3d–4f heterometallic polymer Pr4(H2O)9Cu3.5Cl0.5(Bpdc)6.5(OH)2 · 5H2O (I) (H2Bpdc = 2,2′-bipyridyl-5,5′-dicarboxylic acid) has been hydrothermally synthesized by the reaction of CuCl2 · 2H2O, PrCl3, H2Bpdc, TAA (TAA = 1H-tetrazolyl-1-acetic acid) and glacial acetic acid and characterized by elemental analysis, IR spectroscopy, and single-crystal X-ray diffraction. Single-crystal structural analysis shows that I displays an interesting heterometallic 3D coordination framework constructed from 2D praseodymium-oxygen layers and [Cu(Bpdc)2]3− and [CuCl(Bpdc)]2− pillars. The photofluorescence properties of I have been investigated.

Organic-inorganic hybrid supramolecular architecture constructed from Keggin-type [PMo12O40]3− clusters and transition metal complexes

A Keggin organic-inorganic hybrid polyoxometalate combined with nickel complex [Ni (Dmf)3(H2O)][HPMo12O40] · (Dmf) · 2H2O (I) has been synthesized and structurally characterized by elemental analysis, IR spectrum, TG analysis, cyclic voltammetry, and single-crystal X-ray diffraction. Interestingly, a two-dimensional supramolecular network is constructed by the [PMo12O40]3− polyanions, [Ni(Dmf)3(H2O)]2+ cations, and water molecules via hydrogen-bonding interactions. The cyclic voltammetric measurements illustrate that the [PMo12O40]3− polyanion is the electrochemical redox active center of I in the solution.

Synthesis, crystal structure and properties of a new heptamolybdate (NH4)6H2[Cu(C2O4)2(Mo7O24)] · 9H2O

An interesting heptamolybdate (NH4)6H2[Cu(C2O4)2(Mo7O24)] · 9H2O (I) was prepared by convenational method in an aqueous solution and characterized by IR spectroscopy, elemental analysis, thermogravimetric analysis, X-ray photoelectron spectroscopy and single-crystal X-ray diffraction. Crystal data for I: monoclinic, space group P21/m with a = 10.1460(5), b = 18.2616(9), c = 10.4994(5) Å, β = 94.3410(10)°, and Z = 2. X-ray structure analysis revealed the complexes to contain a copper center in an octahedral coordination mode bound to two [C2O4]2− anios via the oxygen atoms and two oxygen atoms of the new heptamolybdate species. The zigzag chain structure of I is constructed by [Cu(C2O4)2(Mo7O24)] units via Mo-O-Cu-O-Mo linkers.

A novel 2D organic-inorganic hybrid 3d–4f polyoxometalate built by [Gd(α-PW11O39)2]11− units and [Cu(Dap)2]2+ bridges

A novel 2D organic-inorganic hybrid 3d–4f polyoxometalate [Cu(Dap)2(H2O)][Cu(Dap)2]4.5[Gd(α-PW11O39)2] · 5H2O (I) (Dap = 1,2-diaminopropane) built by [Gd(α-PW11O39)2]11− units and [Cu(Dap)2]2+ bridges has been synthesized hydrothermally by the reaction of GdCl3, CuCl2 · 2H2O, Na9[A-α-PW9O34] · 7H2O, and Dap and characterized by elemental analysis, IR spectrum, UV spectrum, powder X-ray diffraction, and single-crystal X-ray diffraction. Single-crystal structural analysis shows that I displays an interesting 2D 3d–4f heterometallic sheet architecture with a 5-connected topology constructed from 1: 2-type [Gd(α-PW11O39)2]11− subunits and [Cu(Dap)2]2+ bridges. To the best of our knowledge, I represents a rare organic-inorganic hybrid 2D 3d–4f heterometallic monovacant Keggin phosphotungstate.