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ABSTRACT: A 12-connected metal-organic framework based on an unprecedented cyclic Cu(12) cluster with a large internal cavity has been prepared, and its cation exchange property was determined.
Chemical Communications 06/2012; 48(58):7295-7. · 6.17 Impact Factor
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ABSTRACT: The reactions of [CuTbL(Schiff)(H(2)O)(3)Cl(2)]Cl complexes with A- or B-type Anderson polyoxoanions lead to new polyoxometalate-supported 3d-4f heterometallic systems with single-molecule-magnet behavior.
Inorganic Chemistry 03/2012; 51(5):2722-4. · 4.60 Impact Factor
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ABSTRACT: Three hybrid networks based on octamolybdate building units, Cu(I)(8)BBTZ(6)[(α-Mo(8)O(26))(β-Mo(8)O(26))] (1), (Cu(I)BBTZ)(4)[Mo(7)Cu(II)O(24)(H(2)O)(2)]·6H(2)O (2), and Cu(II)Cu(I)(2)BBTZ(5)[β-Mo(8)O(26)] (3) (BBTZ = 1,4-bis(1,2,4-triazol-1-ylmethyl)benzene), have been synthesized under ionothermal conditions and structurally characterized by single-crystal X-ray diffraction. 1 exhibits a rare 3D three-fold self-penetration network (SPN) structure, in which the interpenetrating polymer networks (IPN) formed by α-Mo(8)O(26) units, Cu(I) ions and BBTZ ligands are united by β-Mo(8)O(26) units. 2 shows a classic 10(3)-utp net built by transition-metal monosubstitution octamolybdate β-Mo(7)CuO(26), Cu(I) and BBTZ ligands. 3 displays an interesting interpenetrating network (IPN) structure formed by 2D poly-rings layers and 3D NaCl topology framework. IR, TG, and electrochemical studies were also conducted to further authenticate the identities of these compounds. Photocatalytic investigation indicates that compounds 1-3 are active for photocatalytic H(2) evolution under UV irradiation.
Dalton Transactions 01/2012; 41(14):4084-90. · 3.84 Impact Factor
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Yan-fei Qi,
Hong Zhang,
Juan Wang,
Yanfang Jiang,
Jinhua Li,
Ye Yuan,
Shiyao Zhang,
Kun Xu,
Yangguang Li,
Juan Li,
Junqi Niu, Enbo Wang
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ABSTRACT: A structural determined heteropolytungstate, [K(4)(H(2)O)(8)Cl][K(4)(H(2)O)(4)PTi(2)W(10)O(40)]·NH(2)OH 1, has been synthesized and evaluated for in vitro antiviral activities against hepatitis B (HBV) and SARS virus. The identity and high purity of compound 1 were confirmed by elemental analysis, NMR, IR analysis and single-crystal X-ray diffraction. The compound 1, evaluated in HepG 2.2.15 cells expressing permanently HBV, significantly reduced the levels of HBV antigens and HBV DNA in a dose-dependent and time-dependent manner. EC(50) values were determined to be 54μM for HBeAg, 61μM for HBsAg and 2.66μM for supernatant HBV DNA, as compared to 1671, 1570, 169μM, respectively, for the commercially-available hepatitis B drug adefovir dipivoxil (ADV). Intracellular cccDNA, pgRNA and HBcAg were also found to be decreased by compound 1 in a concentration-dependent manner. Cytotoxicity results showed that compound 1 has low toxicity in HepG 2 cells with CC(50) value of 515.20μM. The results indicate that compound 1 can efficiently inhibit HBV replication in HepG 2.2.15 cells line in vitro. Additionally, compound 1 also shows high anti-SARS activity at an EC(50) of 7.08μM and toxicity with a CC(50) of 118.6μM against MDCK cells.
Antiviral research 11/2011; 93(1):118-25. · 3.61 Impact Factor
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ABSTRACT: Two asymmetric polyoxomolybdates Na(6){Mo(2)O(5)[(Mo(2)O(6))NH(3)CH(2)CH(2)CH(2)C(O)(PO(3))(2)](2)}·16H(2)O (1) and (NH(4))(7)Na{MoO(2)[(Mo(2)O(6))NH(3)CH(2)CH(2)CH(2)C(O)(PO(3))(2)]}(4)·H(2)O (2) have been synthesized by the reactions of alendronic acid with molybdate. Structure analysis revealed that the polyoxoanions 1 and 2 can be described as dimeric and tetrameric aggregates of the {MoO(3)[(Mo(2)O(6))NH(3)CH(2)CH(2)CH(2)C(O)(PO(3))(2)]} units respectively. Their tetrabutylammonium salts show efficient selective oxidation of benzyl alcohol to benzaldehyde with 72.5% and 81.5% benzyl alcohol conversion, and 87.1% and 82.4% benzaldehyde selectivity, respectively.
Dalton Transactions 09/2011; 40(33):8414-8. · 3.84 Impact Factor
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ABSTRACT: One new polyoxometalate compound H3(Tea)(Bmim)3[P2W18O62]·3H2O (Tea = triethylamine, Bmim = 1-methyl-3-ethylimidazole) (1) and three new polyoxometalate-based metal−organic frameworks (PMOFs) CuII(Bbi)1.5(H2Bbi)2[P2W18O62] (Bbi = 1,1-(1,4-butanediyl)-bis(imidazole)) (2), CuII2.5(Mimin)(HMimin)(Bbi)3[P2W18O62]·3H2O (Mimin = methylimidazol) (3), and CuII(Bbtz)(H2Bbi)(H2Btp)[P2W18O62] (Bbtz = 1,4-bis(triazol-1-ylmethyl)benzene, Btp = 1,3-Bis(1,2,4-triazol-1-yl)propane) (4) have been synthesized under ionothermal conditions using an ionic liquid (IL) [Bmim]Br (Bmim = 1-ethyl-3-methylimidazole) as solvent. Their structures were determined by single crystal X-ray diffraction. Compound 1 possesses a one-dimensional (1D) supramolecular chain-like structure constructed from [P2W18O62]6− anions, Bmim, Tea, and water molecules. Compound 2 has a two-dimensional (2D) (6,3)-layer structure built by [P2W18O62]6− anions, copper ions, and Bbi ligands. Compounds 3 and 4 are three-dimensional (3D) PMOFs with novel (6.8.10)(4.6.83.10)(4.6.83.12) and classic (65.8)(65.8)-cds topologies, respectively. Compounds 2−4 represent the first examples of PMOFs synthesized by the ionothermal method. The successful synthesis of compounds 2−4 suggests that ionothermal synthesis will be a very promising synthetic technique for assembling new PMOFs. Additionally, the properties of the four compounds have been studied in detail.
01/2011;
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ABSTRACT: By combination of heteropolymolybdates and metal-Schiff-base complexes, two new organic-inorganic hybrid compounds {Mn(salen)(2)(H(2)O)(2)[AlMo(6)(OH)(6)O(18)]}[arg]·16H(2)O (1) and {Mn(salen)(2)(H(2)O)(2)[CrMo(6)(OH)(6)O(18)]}[arg]·11H(2)O (2) (salen = N,N'-ethylene-bis(salicylideneiminate) have been successfully isolated. Compounds 1 and 2 were structurally characterized by elemental analyses, IR spectra, thermogravimetric analysis, and single-crystal X-ray diffraction. To the best of our knowledge, compounds 1 and 2 represent the first single-crystal structures of metal-Schiff-base decorated polyoxometalates (POMs) compounds. Photocatalytic experiments indicated that both 1 and 2 exhibit high catalytic activity for photodegradation of RhB with UV irradiation. In addition, the magnetic properties of 1 were also investigated.
Dalton Transactions 01/2011; 40(1):56-61. · 3.84 Impact Factor
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ABSTRACT: In this article, we have synthesized two new heteropolytungstate-based compounds [EMIM]4[SiW12O40] (1) and [EMIM]6[P2W18O62] · 4H2O (2) using the ionic liquid (IL) [EMIM]Br (EMIM = 1-ethyl-3-methylimidazolium) as a solvent and characterized them by infrared (IR) and ultraviolet (UV) spectra, thermogravimetric (TG) and elemental analyses, electrochemistry, and single-crystal X-ray analyses. Compound 1 is constructed from one [SiW12O40]4− and four [EMIM]+. In the structure, [SiW12O40]4− and [EMIM]+ are connected by hydrogen bonds with the surface oxygens of the polyoxoanion to form a 3-D supramolecular framework. The heteropolyanion of 2 is a classical Dawson-type structure [P2W18O62]6− and connected with six cations through hydrogen bonds. The structures of these two heteropolyanions are consistent with those synthesized by traditional methods, indicating that ionothermal synthesis is an effective method for the preparation of heteropolyoxometalates. The photocatalytic properties of these compounds have also been investigated.
Journal of Coordination Chemistry. 06/2010; 63(11):1833-1843.
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ABSTRACT: In the large polyoxometalate (POM) family, rare-earth polyoxometalate (RE-POM) complexes form one of the most-interesting subgroups. The RE-POM complexes display a huge diversity of structure including various sized RE-POM cluster, extending structural RE-POM polymer and RE-organo cation POM supermolecule complex. Moreover, RE-POM complexes may combine the intrinsic properties of both constituents. RE ions can impart useful functionality such as luminescence, magnetic or Lewis acid catalytic centers to POM, thus extending their range of physical and chemical properties and gaining new potential applications in material science, catalysis and medicine.
04/2010: pages 193 - 228; , ISBN: 9780470824870
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ABSTRACT: A unique three-dimensional metal−organic framework (MOF) [Cd4(1,10′-phen)(fum)(S-mal)(R-mal)(H2O)] (1) (1,10′-phen =1,10-phenanthroline, fum = fumarate dianion, mal = malate dianion) has been synthesized and characterized by single-crystal X-ray analysis. Under hydrothermal conditions, after a “three birds with one stone” in situ reaction process, maleic acid turns into fumarate dianion, isomeric R-malate dianion and S-malate dianion, which further connect with Cd atoms and form an octanuclear Cd cluster. The octanuclear Cd cluster links with neighboring clusters and constructs a rod-shaped secondary building unit (SBU). Neighboring rod-shaped SBUs are further connected by fumarate dianions and thus forms a three-dimensional network. To our interests, complex 1 exhibits interesting semiconductivity and fluorescence properties. When citraconic acid was used instead of maleic acid, a new complex [Cd2(mesac)2(1,10′-phen)2] (2) (mesac = mesaconate dianion) was synthesized under about the same reaction conditions. Complex 2 also exhibits fluorescence properties.
04/2010;
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ABSTRACT: The reaction of Cl(3)Sn(CH(2))(2)COOCH(3), [H(2)P(2)W(12)O(48)](12-) and WO(4)(2-) in acetate buffer solution led to the hydrolysis of estertin into a carboxyethyltin group and the assembly of a new tetra(organotin)-decorated boat-like polyoxometalate.
Dalton Transactions 04/2010; 39(14):3369-71. · 3.84 Impact Factor
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ABSTRACT: Reactions of hexavacant polyoxotungstates [H(2)P(2)W(12)O(48)](12-) ({P(2)W(12)}) with transition-metal (TM), and alkali-metal ions lead to the isolation of two hexa-TM-containing polyoxotungstates Na(15)[Na(3) subset {M(H(2)O)(4)}(6){WO(H(2)O)}(3)(P(2)W(12)O(48))(3)].xH(2)O (M = Co(2+), x = 109 for 1; M = Ni(2+), x = 110 for 2). Single-crystal X-ray diffraction analysis revealed that compounds 1 and 2 both crystallized in the orthorhombic system, space group Cmcm, with lattice constants a = 21.353(3) A, b = 32.114(3) A, c = 33.848(4) A, for 1; a = 21.643(6) A, b = 31.870(6) A, c = 33.861(7) A for 2. Polyoxoanions [Na(3) subset {M(H(2)O)(4)}(6){WO(H(2)O)}(3)(P(2)W(12)O(48))(3)](15-) in 1 and 2 exhibit a crown-type structure composed of a [{WO(H(2)O)}(3)(P(2)W(12)O(48))(3)](18-) (abbreviated as {P(6)W(39)}) shell encapsulating six TM ions and three Na(+) cations. Polyoxoanions 1 and 2 represent the first hexa-TM-containing {P(2)W(12)}-based trimeric POMs, which offer new examples with the potentially aqua-ligand-induced capability of "trapping" metal ions in the {P(6)W(39)} shell. Electrocatalytic studies show that compounds 1 and 2 display electrocatalytic activity to reduce nitrite.
Dalton Transactions 04/2010; 39(16):3884-9. · 3.84 Impact Factor
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ABSTRACT: Two new cantilever-type polyoxometalates Na(5)(NH(4)){V(IV)[(Mo(2)O(6))CH(3)C(O)(PO(3))(2)](2)}.13H(2)O (1) and (NH(4))(4){V(IV)[(Mo(2)O(6))NH(3)CH(2)CH(2)CH(2)C(O)(PO(3))(2)](2)}.6H(2)O (2) have been synthesized and characterized by IR spectroscopy, UV-visible spectroscopy, elemental analysis, TG analysis, XPS, (31)P NMR and single-crystal X-ray diffraction. The structure analysis reveals that the diphosphonate, hydroxyethylidene diphosphonic acid and alendronic acid as the scaffolds, have been grafted on the "S"-shaped polyoxoanions and respectively. The alkyl groups of the diphosphonates like arms hanged on the polyoxoanions form the cantilever-type polyoxometalates.
Dalton Transactions 02/2010; 39(5):1245-9. · 3.84 Impact Factor
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ABSTRACT: Ionothermal synthesis was applied to the formation of polyoxometalates (POMs) and two new compounds [EMIM](8)Na(9)[WFe(9)(micro(3)-O)(3)(micro(2)-OH)(6)O(4)H(2)O(SiW(9)O(34))(3)].7H(2)O (, [EMIM](8)Na(9)[].7H(2)O, EMIM = 1-ethyl-3-methylimidazolium) and [EMIM](4)[SiMo(12)O(40)].12H(2)O (), have been successfully produced in the ionic liquid (IL) [EMIM](4)Br. They were characterized by single-crystal X-ray diffraction, elemental analysis, UV-vis, IR and TG analysis. Furthermore, the magnetic properties of and the electrochemical properties of were studied. is a high-nuclear transition metal substituted polyoxometalate (TMSP) and the unprecedented polyoxoanion of is composed of three [alpha-SiW(9)O(34)](10-) Keggin moieties connected by a {WFe(9)} cluster core. is a heteropolyoxometalate with the polyoxoanion of alpha-Keggin type.
Dalton Transactions 02/2010; 39(7):1740-4. · 3.84 Impact Factor
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ABSTRACT: Two organic–inorganic hybrid materials built from copper–glycin complexes and paradodecatungstates, Na6[{Cu(gly)(H2O)}]2[{Cu(H2O)}(H2W12O42)] 21H2O (1) and Na{Na(H2O)6}{Na(H2O)4}3[{Cu(gly)2}]2{H5(H2W12O42)} 8.5H2O (gly = glycin) (2), have been synthesized in aqueous solution and characterized by IR, UV, TG, elemental analysis, electrochemistry, and single-crystal X-ray analyses. In 1, [H2W12O42]10− building block connects two neighboring clusters with [Cu(H2O)]2+ groups to produce an infinite 1-D chain; then these chains are linked through [Cu(gly)(H2O)]+ groups to form a 2-D layer structure, which is further joined by Na+ to form a 3-D network. In 2, [H2W12O42]10− decorated by two [Cu(gly)2] moieties connects four adjacent clusters with six Na+ into a 2-D layer. In addition, luminescence and photocatalysis properties of these compounds have been investigated.
Journal of Coordination Chemistry. 01/2010; 63(1):26-35.
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ABSTRACT: Reactions of hexavacant polyoxotungstate [H2P2W12O48]12− ({P2W12}) with transition-metal and lanthanide-metal cations assisted with organic molecules (tartrate or dimethylammonium chloride) lead to the isolation of two polyoxotungstates: K3Na8[K3{GdMn(H2O)10}{HMnGd2(Tart)O2(H2O)15}{P6W42O151(H2O)7}]·44H2O (1) and K3Na10[K3{GdCo(H2O)11}2{P6W41O148(H2O)7}]·43H2O (2). Single-crystal X-ray diffraction analyses reveal that both 1 and 2 contain a crown-type polyoxoanion shell [{WO(H2O)}3(P2W12O48)3]30− ({P6W39}), which consists of three {P2W12} units connected by three {WO(H2O)} linkers. Compound 1 has a two-dimensional porous framework constructed from 3d-4f cluster-containing {P6W39} aggregates and mixed 3d and 4f linkers. Compound 2 exhibits a one-dimensional chain-like structure composed of di-Co-containing {P6W39} aggregates and {Gd(H2O)7}3+ bridging units. Magnetic studies of compounds 1 and 2 indicate that antiferromagnetic interactions exist in these two compounds.
11/2009;
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ABSTRACT: A 1-D ladder-like aggregate, K2Na6[Na(H2O)Fe2(H2O)8(P5W30O110)] · 23.5H2O (1; K2Na6[1a] · 23.5H2O) has been obtained by conventional aqueous solution reaction. X-ray diffraction analysis reveals that 1 crystallizes in the monoclinic system, space group P 2 1 /m, a = 16.938(3) Å, b = 21.396(4) Å, c = 17.520(4) Å, β = 98.14(3)°, V = 6285(2) Å3, and Z = 2. Polyoxoanion 1a shows a 1-D ladder-like chain, built up of Preyssler anion and Fe3+ linkers, which represents the first extended structure based on Preyssler anion and transition metal linkers. The 1-D chains in 1 are further connected into a 3-D open framework by potassium and sodium cations. Compound 1 displays electrocatalytic activity towards the reduction of nitrite.
Journal of Coordination Chemistry 10/2009; 62(20):3259-3267. · 1.55 Impact Factor
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ABSTRACT: Five compounds based on [MnMo(9)O(32)](6-): (Himi)(6)[MnMo(9)O(32)] (1) (imi=imidazole), Na(2)(Himi)(4)[MnMo(9)O(32)]2 H(2)O (2), Na(3)(Himi)(3)[MnMo(9)O(32)] (3), D-NH(4)Mn(2.5)[MnMo(9)O(32)]11 H(2)O (4 a), and L-NH(4)Mn(2.5)[MnMo(9)O(32)]11 H(2)O (4 b) were prepared and characterized. X-ray crystallographic analysis revealed that compounds 1 and 2 with imidazole molecules as linkers are racemic compounds; compound 3 is a racemic solid solution of Na(+) cations and the polyoxoanion [MnMo(9)O(32)](6-); and compounds 4 a and 4 b are enantiomers. In compound 4, the homochiral polyoxoanions [MnMo(9)O(32)](6-) are connected by Mn(2+) cations to form a unique (4(5)6)(4(7)6(8)) topology net framework. By adjusting the linkers from imidazole molecules to Na(+) and finally Mn(2+) cations, the chiral polyoxoanions [MnMo(9)O(32)](6-) were changed from a racemic compound to a conglomerate. This means that spontaneous resolution can be efficiently realized by connecting homochiral polyoxoanions into one-dimensional (1D), 2D, and 3D structures, with an emphasis on using appropriate linkers with substantial interaction strength, directionality, and enantioselectivity.
Chemistry 10/2009; 15(41):10940-7. · 5.93 Impact Factor
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ABSTRACT: We have synthesized four coordination polymers with two different nitrogen containing organic ligands and different lanthanide metal ions, under hydrothermal condition. [{Ln2(bpdc)3(H2O)2}] n (Ln = Dy (1), Sm (2)) (bpdc = 2,2-bipyridine-3,3-dicarboxylic acid) are isostructural, with 2-D supramolecular layer structure composed from 1-D chains. Like 1 and 2, [{Ln(pzda)2(H2O)2} · 4H2O] n (Ln = Dy (3), Nd (4)) (pzda = pyrazine-2,6-dicarboxylic acid) are also isostructural with 1-D chain-like structures. The photoluminescence of 2 is studied.
Journal of Coordination Chemistry 09/2009; 62(17):2755-2763. · 1.55 Impact Factor
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ABSTRACT: A series of novel organic-inorganic assemblies, {Ag(3)(2,2'-bipy)(2)(4,4'-bipy)(2)}{Ag(2,2'-bipy)(2)}{Ag(2,2'-bipy)}[AlW(12)O(40)].H(2)O (), [Ag(phen)(2)](3)[Ag(phen)(3)][AlW(12)O(40)].H(5)O(2) () and {Co(2,2'-bipy)(3)}(3){Co(H(2)O)(2,2'-bipy)(2)[AlW(12)O(40)]}(2).H(2)O () (2,2'-bipy = 2,2'-bipyridine, 4,4'-bipy = 4,4'-bipyridine, phen = 1,10-phenanthroline) constructed from Keggin-type [AlW(12)O(40)](5-) polyoxoanion and transition-metal organoamine subunits, have been hydrothermally synthesized and characterized by elemental analysis, IR spectroscopy, thermal gravimetric analysis (TGA), electrochemical properties and single-crystal X-ray diffraction. A remarkable aspect of compound 1 is that there exists four types of coordination configurations for the five crystallographically independent Ag centers, and this phenomenon has never been observed in polyoxometalate (POM) chemistry. The trimeric {[Ag(phen)(2)](3)}(3+) cluster in compound 2 is firstly extended into an interesting one-dimensional wave-like array and then is further extended into a three-dimensional supramolecular network with the [AlW(12)O(40)](5-) clusters residing in the interstices of this three-dimensional framework. The most striking structure feature of compound 3 is that three water molecules linearly arrange between the adjacent monosupporting {Co(H(2)O)(2,2'-bipy)(2)[AlW(12)O(40)]}(3-) anions, leading to the formation of the three-dimensional supramolecular network by weak interactions.
Dalton Transactions 07/2009; · 3.84 Impact Factor
