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ABSTRACT: The nona-Cu(II)-containing tungstoarsenate(iii) [H4{Cu(II)9As(III)6O15(H2O)6}(α-As(III)W9O33)2](8-) () has been synthesized and characterized. Polyanion comprises a unique, cylindrical {Cu(II)9As(III)6O15(H2O)6}(6+) cluster, which forms a large central cavity and is capped on either end by an [α-As(III)W9O33](9-) capping group. It exhibits remarkable activity against K562 leukaemia cells, as well as induces HepG2 cell apoptosis and autophagy.
Chemical Communications 04/2013; · 6.17 Impact Factor
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ABSTRACT: 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.
Dalton Transactions 01/2013; · 3.84 Impact Factor
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ABSTRACT: A cage-like {[Ca(H(2)O)](6)(H(2)O)}(12+) cluster with a water molecule enwrapped, sandwiched by two novel [As(4)W(6)O(34)](12-) fragments, has been obtained, and the extension of these clusters from molecules into a 2-D layer occurs through [Ca(H(2)O)(5)](2+) linkers, which represents the first heteropolyoxoanion (HPA) constituted by [As(4)W(6)O(34)](12-) and the unprecedented high nuclearity {[Ca(H(2)O)](6)(H(2)O)}(12+) cluster.
Dalton Transactions 11/2012; · 3.84 Impact Factor
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ABSTRACT: Three organic-inorganic hybrid copper-lanthanide heterometallic germanotungstates, {[Cu(en)(2)(H(2)O)] [Cu(3)Eu(en)(3)(OH)(3)(H(2)O)(2)](α-GeW(11)O(39))}(2)·11H(2)O (1), {[Cu(en)(2)(H(2)O)][Cu(3)Tb(en)(3)(OH)(3)(H(2)O)(2)](α-GeW(11)O(39))}(2)·11H(2)O (2) and {[Cu(en)(2)(H(2)O)][Cu(3)Dy(en)(3)(OH)(3)(H(2)O)(2)](α-GeW(11)O(39))}(2)·10H(2)O (3) and three polyoxometalate hybrids built by lanthanide-containing germanotungstates and copper-ethylendiamine complexes, Na(2)H(6)[Cu(en)(2)(H(2)O)](8){Cu(en)(2)[La(α-GeW(11)O(39))(2)](2)}·18H(2)O (4), K(4)H(2)[Cu(en)(2)(H(2)O)(2)](5)[Cu(en)(2)(H(2)O)](2)[Cu(en)(2)](2){Cu(en)(2)[Pr(α-GeW(11)O(39))(2)](2)}·16H(2)O (5) and KNa(2)H(7)[enH(2)](3)[Cu(en)(2)(H(2)O)](2)[Cu(en)(2)](2){Cu(en)(2)[Er(α-GeW(11)O(39))(2)](2)}·15H(2)O (6) (en = ethylenediamine) have been hydrothermally synthesized and structurally characterized by elemental analyses, inductively coupled plasma atomic emission spectrometry (ICP-AES) analyses, IR spectra, powder X-ray diffraction (PXRD), X-ray photoelectron spectroscopy (XPS) and single-crystal X-ray diffraction. 1-3 are essentially isomorphous and their main skeletons display the interesting dimeric motif {[Cu(3)Ln(en)(3)(OH)(3)(H(2)O)(2)](α-GeW(11)O(39))}(2)(4-), which is constructed from two {Cu(3)LnO(4)} cubane anchored monovacant [α-GeW(11)O(39)](8-) fragments through two W-O-Ln-O-W linkers. The primary backbones of 4-6 exhibit the tetrameric architecture {Cu(en)(2)[Ln(α-GeW(11)O(39))(2)](2)}(24-) built by two 1:2-type [Ln(α-GeW(11)O(39))(2)](13-) moieties and one [Cu(en)(2)](2+) bridge, albeit they are not isostructural. To our knowledge, 1-6 are rare polyoxometalate derivatives consisting of copper-lanthanide heterometallic/lanthanide germanotungstate fragments. 1 exhibits antiferromagnetic coupling interactions within the {Cu(3)EuO(4)} cubane units, while 2 and 3 display dominant ferromagnetic interactions between the Tb(III)/Dy(III) and Cu(II) cations. The room-temperature solid-state photoluminescence properties of 1-3 have been investigated.
Dalton Transactions 07/2012; 41(35):10740-51. · 3.84 Impact Factor
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ABSTRACT: A novel strawberry-like organic-inorganic hybrid, {Na(H(2)O)(3)[Lu(pydc)(H(2)O)(3)](3)}[SiW(12)O(40)]·26.5H(2)O (H(2)pydc = pyridine-2,6-dicarboxylate) containing an intriguing trinuclear lutetium cluster {Na(H(2)O)(3)[Lu(pydc)(H(2)O)(3)](3)}(4+) has been synthesized and its luminescent properties, IR, UV, TG, PXRD analyses and single crystal X-ray diffraction were investigated.
Dalton Transactions 06/2012; 41(33):9885-8. · 3.84 Impact Factor
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ABSTRACT: An organic-inorganic hybrid Keggin compound, [4,4′-bipyH2][4,4′-bipyH]2[VW12O40] · 4,4′-bipy · 7.5H2O (bipy-bipyridine) (1), has been prepared under hydrothermal conditions and characterized by IR spectroscopy, single crystal X-ray diffraction,
thermal analysis, and ESR spectroscopy. 1 crystallized in the monoclinic space group P21/c with a = 18.7350(15) Å, b = 14.0253(12) Å, c = 26.434(2) Å, β= 105.0810(10)°, V = 6706.6(10) Å3 and Z = 4. The crystal structure of 1 consists of diprotonated and monoprotonated 4,4′-bipyridine cations, free 4,4′-bipyridine molecule, lattice water molecules,
and a typical Keggin-type polyoxoanion [VW12O40]4−. The polyoxoanion is constructed by four {W3O16} trinuclear groups, each of which is made up of three edge-sharing {WO6} octahedra, and the {VO4} tetrahedron is in the center of the cage.
Russian Journal of Inorganic Chemistry 05/2012; 54(3):403-406. · 0.41 Impact Factor
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ABSTRACT: A novel organic–inorganic hybrid polyoxoniobate K8Na2{[Cu(en)(H2O)]2 [HNb6O19]2}·25H2O (en=ethylenediamine) 1 has been synthesized by the diffusion method and structurally characterized by elemental analyses, IR, UV-Vis spectra, thermogravimetric
(TG) analysis and single crystal X-ray diffraction. The structure analysis indicates that 1 consists of two {[Cu(en)(H2O)][HNb6O19]}5− polyoxoanions linked each other by two methane-like {K4Na}5+ cationic clusters. Surface photovoltage spectroscopy (SPS) and electric field induced surface photovoltage spectroscopy (EFISPS)
measurements indicate that 1 is the n-type conduction characteristic. Insitu UV and CV studies indicate that 1 can stably exist in the larger pH ranges in aqueous solution.
KeywordsOrganic–inorganic hybrid-Polyoxoniobate-Crystal structure-Linqvist-type
Journal of Cluster Science 04/2012; 21(2):121-131. · 0.92 Impact Factor
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ABSTRACT: Building functional cages: The first lanthanide-containing organodiphosphonate-functionalized polyoxomolybdate cages have been prepared. They exhibit interesting photocatalytic properties in the decomposition of organic dyes.
Chemistry 04/2012; 18(22):6759-62. · 5.93 Impact Factor
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ABSTRACT: A novel yttrium (III) coordination compound supported by plenary Dawson cluster, [Y(NMP)5(H2O)2] [Y(NMP)4(H2O)2(P2Mo18O62)] · NMP · 5.5 H2O, (NMP = N-methyl-2-pyrrolidone) has been synthesized by reaction of α-H6P2Mo18O62 · nH2O, Y2O3 and NMP in water. The results of the single crystal X-ray diffraction analyses show the title compound forms a neutral and
discrete cluster through [P2Mo18O62]6−] being coordinated to [Y(NMP)4(H2O)2]3+ through its terminal oxygen atom.
Chinese Science Bulletin 04/2012; 48(23):2585-2588. · 1.32 Impact Factor
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ABSTRACT: Two novel trivacant Keggin-type polyoxometallate-based manganese carbonyl derivatives K(8)[(OC)(3)Mn(A-α-H(2)GeW(9)O(34))]·10H(2)O (1) and K(8)[(OC)(3)Mn(A-α-H(2)SiW(9)O(34))]·11H(2)O (2) have been synthesized by degradation of the metastable [γ-XW(10)O(36)](8-) (X = Ge(IV), Si(IV)) in CH(3)CN-H(2)O solvent (1 : 2, vol.) and structurally characterized by elemental analyses, IR spectra, thermogravimetric analysis, and single-crystal X-ray diffraction. X-ray diffraction analyses indicate that 1 and 2 are isomorphic and consist of a [(OC)(3)Mn](+) group and a trivacant [A-α-H(2)XW(9)O(34)](8-) fragment, which exhibit the first examples of trivacant Keggin-type metal carbonyl derivatives. Additionally, the electrocatalytic properties of both for NO(2)(-) oxidation have been investigated.
Dalton Transactions 03/2012; 41(19):5832-7. · 3.84 Impact Factor
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ABSTRACT: Four di-Cu(II)-substituted sandwich-type germanomolybdates, (H(2)en)(2)H(7){[Na(0.5)(H(2)O)(3.5)](2)[Cu(2)(β-Y-GeMo(9)O(33))(2)]}·6H(2)O (1), (H(2)en)(2)H{[Na(2.5)(H(2)O)(12)](2)[Cu(en)(2)][Cu(2)(β-Y-GeMo(9)O(33))(2)]}·8H(2)O (2), [Na(4)(H(2)O)(12)](2)H(4)[Cu(2)(β-Y-GeMo(9)O(33))(2)]}·11H(2)O (3) and [Cu(en)(2)](2)[Cu(en)(2)(H(2)O)](2){[Cu(en)(2)](2)[Cu(2)(β-Y-GeMo(9)O(33))(2)]}·8H(2)O (4) (en = ethylenediamine), have been prepared. It is interesting that 1-3 were obtained in the same aqueous solution reaction system but exhibited different structures: 1 displays a 0D structure, 2 shows an organic-inorganic 1D chain structure, while 3 displays a 2D network. 4 was synthesized under hydrothermal condition by the same reagents, which represents the first transition metal-sandwiched organic-inorganic 2D heteropolymolybdate.
Dalton Transactions 03/2012; 41(17):5235-40. · 3.84 Impact Factor
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ABSTRACT: Two types of novel oxalate-bridging rare-earth-substituted Keggin-type phosphotungstates {[(α-PW(11)O(39)) RE(H(2)O)](2)(C(2)O(4))}(10-) (RE = Y(III) for 1, Dy(III) for 2, Ho(III) for 3 and Er(III) for 4) and {(α-x-PW(10)O(38))Tm(2)(C(2)O(4))(H(2)O)(2)}(3-) for 5 have been synthesized by reaction of [α-PW(11)O(39)](7-) with RE cations and oxalate ligands in aqueous solution. They have been further characterized by elemental analyses, X-ray powder diffraction (XRPD), IR spectra, thermogravimetric (TG) analysis, and single-crystal X-ray diffraction. The common features of 1-4 are that they all contain the dimeric mono-RE substituted Keggin [RE(α-PW(11)O(39))](2)(14-) subunits linked by oxalate ligands whereas 5 exhibits a one-dimensional (1D) chain architecture built by the unusual divacant [α-x-PW(10)O(38)](11-) polyoxoanions and oxalate ligands. Notably, 1-5 represent the first oxalate-bridging dimers constructed by lacunary Keggin phosphotungstate-supported RE derivatives, and the unusual divacant [α-x-PW(10)O(38)](11-) fragment is found for the first time. Furthermore, the room-temperature solid-state photoluminescence of 2 has been investigated. Variable-temperature magnetic susceptibility measurements indicate that 2 and 4 demonstrate weak ferromagnetic couplings within the two adjacent RE cations bridged through oxalate ligands, whereas dominant antiferromagnetic interactions are observed in 3 and 5, respectively.
Dalton Transactions 03/2012; 41(13):3764-72. · 3.84 Impact Factor
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ABSTRACT: Five rare-earth-transition-metal (RE-TM) heterometal organic-inorganic hybrids based on Keggin-type silicotungstates and mixed ligands H2pzda (pzda=pyrazine-2,3-dicarboxylate) and en (en=ethylenediamine) (enH2)[Cu(en)2(H2O)]2{[Cu(en)2][Cu(en)2(H2O)][(α-SiW11 O39)RE(H2O)(pzda)]}2·n H2O (n≈4; RE=YIII (1), DyIII (2), YbIII (3), and LuIII (4)) and [Cu(en)2(H2O)]2{[Cu(en)2]2[Cu(pzda)2][(α-H2SiW11O39)Ce(H2O)]2}·n H2O (5; n≈8) have been hydrothermally synthesized and structurally characterized. Compounds 1-5 all contain the dimeric mono-RE substituted Keggin [RE(α-SiW11O39)]210- subunits linked by H2pzda ligands. Interestingly, 1-4 exhibit discrete structures, in which the H2pzda ligand acts as a tetradentate ligand to bind the RE and Cu cations, whereas 5 displays a 1D double-chain architecture, in which the H2pzda ligand adopts a new pentadentate mode to connect the Ce and Cu cations. To our knowledge, 1-5 represent the first monovacant Keggin-type silicotungstates containing both RE-TM heterometals and mixed ligands. The luminescence of 2 is derived from the combination of the DyIII cations and H2pzda ligands, whereas the luminescence properties of 1 and 3-5 are attributable to the H2pzda ligands.
Chemistry - An Asian Journal 02/2012; 7(5):966-74. · 4.50 Impact Factor
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ABSTRACT: Three novel octatungstate-supported tricarbonyl metal derivatives have been synthesized and characterized, which represent the first examples of isopolyoxotungstates-supported carbonyl metal compounds.
Dalton Transactions 09/2011; 40(33):8298-300. · 3.84 Impact Factor
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ABSTRACT: A series of organic–inorganic hybrid polyoxometalate derivatives {[Cu(en)2]1.5[Cu(en)(2,2′-bipy)(H2O)n]Ce[(α-PW11O39)2]}6– [(Ln, n) = (CeIII, 0) for 1, (PrIII, 1) for 2)], {[Cu(en)2]2(H2O)[Cu(en)(2,2′-bipy)]Ln[(α-HPW11O39)2]}4– [Ln = GdIII for 3, TbIII for 4, ErIII for 5] and {[Cu(en)2]1.5[Cu(en)(2,2′-bipy)]Nd[(α-H5PW11O39)2]}3– for 6 (2,2′-bipy =2,2′-bipyridine and en = ethylenediamine) have been successfully synthesized under hydrothermal conditions and further characterized by elemental analyses, inductively coupled plasma (ICP) analyses, X-ray powder diffraction (XRPD), IR spectra, UV spectra, electron paramagnetic resonance (EPR) spectra, thermogravimetric (TG) analyses, and single-crystal X-ray diffraction. The common features of 1–6 are that they all consist of sandwich-type [Ln(α-PW11O39)2]11– polyoxoanions as the fundamental building blocks and copper coordination cations as bridges. 1 and 2 show the 1-D zigzag chains, and 3–5 exhibit the unprecedented 2-D structures built by [Ln(α-PW11O39)2]11– polyoxoanions and [Cu(en)2]2+ and [Cu(en)(2,2′-bpy)]2+ cations, whereas 6 displays the scarce 3-D framework with a (46·64) topology. As expected, 1–6 contain two types of organic ligands. Furthermore, the photocatalysis properties of rhodamine-B (RhB) upon a 500 W Hg lamp irradiation in the presence of 1, 2, 3, 4, 5, or 6 have been examined. The photoluminescence property of 4 has been investigated.
07/2011;
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ABSTRACT: Three novel transition-metal substituted polyoxotungstates based on Keggin fragments, Cs3K3[Co(H2O)6]2[Co(H2O)3(α-GeW11CoO38)3]·30H2O (1), K18{[Mn(H2O)3]2[Mn(H2O)2][(B-β-SiW9O33(OH))Mn3(H2O)(B-β-SiW8O30(OH))]2}·16H2O (2), and K8[Cd(H2O)3]2[Cd4(H2O)2(B-α-SiW9O34)2]·20H2O (3), have been synthesized by reaction of dilacunary Keggin precursors K8[γ-GeW10O36]·6H2O/K8[γ-SiW10O36]·12H2O with transition-metal salts at ambient temperature and characterized by inductively coupled plasma (ICP) analyses, IR spectra, UV spectra, and single-crystal X-ray diffraction. The polyoxoanion of 1 is a novel trimer constructed from three mono-CoII substituted Keggin fragments [α-GeW11CoO38]4− linked by six W−O−Co/W bridges and a capping [Co(H2O)3]2+ bridge. 2 displays the one-dimensional chain built by tetrameric {[Mn(H2O)3]2[Mn(H2O)2][(B-β-SiW9O33(OH))Mn3(H2O)(B-β-SiW8O30(OH))]2}18− units, which is the first one-dimensional silicotungstate containing asymmetric sandwich-type moieties constructed from [B-β-SiW9O34]10− and [B-β-SiW8O31]10− fragments. 3 utilizes the two-dimensional sheet established by tetra-CdII substituted sandwich-type [Cd4(H2O)2(B-α-SiW9O34)2]12− units and [Cd(H2O)3]2+ linkers, representing the first two-dimensional (3,6)-topological network with a Schläfli symbol of 364653 built by sandwich-type Keggin units in polyoxometalate chemistry. Magnetic susceptibility measurements indicate antiferromagnetic exchange interactions within CoII ions in 1 and within MnII ions in 2. The best least-squares fitting values for 2 are J = −1.16 cm−1 and g = 2.13 based on the isostropic spin model. Furthermore, the room-temperature solid-state photoluminescence of 3 displays two emission bands, which are derived from O → Cd ligand-to-metal charge transfer transitions and O → W ligand-to-metal charge transfer transitions, respectively.
03/2011;
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ABSTRACT: Three novel inorganic−organic hybrid arsenomolybdates constructed from monocapped trivacant [AsIIIAsVMo9O34]6− fragments with [Cu(en)2]2+ or [Cu(dap)2]2+ linkers, [Cu(en)2H2O]2{[Cu(en)2][Cu(en)2AsIIIAsVMo9O34]}2·4H2O (1), (H2en)1.5[Cu(en)(Hen)][AsIIIAsVMo9O34]·2H2O (2) (en = ethylenediamine), and [Cu(dap)2]4[Cu(dap)2(H2O)][Cu(dap)2(AsIIIAsVMo9O34)2]·2H2O (3) (dap = 1,2-diaminopropane), have been successfully synthesized under hydrothermal conditions and structurally characterized by elemental analyses, IR spectra, single-crystal X-ray diffraction, and thermogravimetric (TG) analysis. Single-crystal structural analyses indicate that 1−3 all contain the peculiar monocapped trivacant [AsIIIAsVMo9O34]6− subunit derived from the infrequent trivacant Keggin [A-α-AsVMo9O34]9− fragment with a capping {AsO3} group. Notably, 1−3 represent rare inorganic−organic hybrid heteropolymolybdate (HPM) containing [AsIIIAsVMo9O34]6− subunits, which display the assembly from a zero-dimensional sandwich-type dimer, one-dimensional chain, to a two-dimensional layer by the [Cu(en)2]2+ or [Cu(dap)2]2+ linkers. Surface photovoltage spectroscopy (SPS) and electric field induced surface photovoltage spectroscopy (EFISPS) measurements for 1−3 indicate that only 3 has the n-type semiconductor characteristic.
01/2011;
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ABSTRACT: A new organic–inorganic hybrid polyoxoniobate (H2en)2[Ni(en)3][H2Nb6O19] · 5.5H2O (1) (en = ethylenediamine) has been synthesized by the diffusion method and structurally characterized by elemental analyses, infrared spectrum, ultraviolet (UV) spectroscopy, X-ray photoelectron spectroscopy (XPS), X-ray powder diffraction, thermogravimetric (TG) analysis, and single-crystal X-ray diffraction. Crystal structure analysis reveals that 1 exhibits a 3-D supramolecular architecture constructed from Lindqvist-type [H2Nb6O19]6− polyoxoanions and [Ni(en)3]2+ via hydrogen-bonding interactions. The XPS measurement indicates that the oxidation state of Ni is +2. TG curve of 1 exhibits two steps of weight loss. In situ UV spectra display that 1 can exist in large pH range in aqueous solution.
Journal of Coordination Chemistry 11/2010; 63(21):3753-3763. · 1.55 Impact Factor
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ABSTRACT: A novel organic−inorganic hybrid phosphovanado-molybdate Na(H2O)6[Cu(2,2′-bipy)3]2[Cu(1,2-dap)2(H2O)]6H[Cu(1,2-dap)2{PMoVI8VIV4O40(VIVO)2Cu(1,2-dap)2}]6·2H2O (1) (1,2-dap = 1,2-diaminopropane, 2,2′-bipy = 2,2′-bipyridine) has been hydrothermally synthesized and characterized by elemental analyses, IR, TG-DTA, X-ray photoelectron spectroscopy (XPS), X-ray powder diffraction (XRPD), and single crystal X-ray diffraction. Interestingly, 1 represents the first example of cyclohexane-like ring-shaped phosphovanadomolybdate constructed from six bicapped pseudo-Keggin clusters [PMoVI8VIV4O40(VIVO)2Cu(1,2-dap)2]5− linked by six [Cu(1,2-dap)2]2+ linkers. Notably, adjacent rings are connected together, forming the 3-D supramolecular structure through hydrogen bonding interactions.
09/2010;
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ABSTRACT: By introducing mixed ligands into the hexaniobate system, three novel organic−inorganic hybrids, [Cu(en)2]2{[Cu(1,10-phen)][Cu(1,10-phen)(H2O)]Nb6O19}·10.5H2O (1), [Cu(en)2]2{[Cu(2,2′-bipy)][Cu(2,2′-bipy)(H2O)]Nb6O19}·9H2O (2) and [Cu(1,2-dap)2]2{[Cu(2,2′-bipy)][Cu(2,2′-bipy)(H2O)]Nb6O19}·11H2O (3) (en = ethylenediamine, 1,10-phen = 1,10-phenanthroline, 2,2′-bipy = 2,2′-bipydine, 1,2-dap = 1,2-diaminopropane), have been synthesized by the solution diffusion method and characterized by elemental analyses, IR spectra, UV spectroscopy, thermogravimetric analyses, and single-crystal X-ray diffraction. 1, 2, and 3 can be formularized as [Cu(L1)2]2{[Cu(L2)][Cu(L2)(H2O)]Nb6O19}·nH2O (L1 = en for 1 and 2, 1,2-dap for 3, L2 = 1,10-phen for 1, 2,2′-bipy for 2 and 3, n = 10.5 for 1, 9 for 2, 11 for 3), and all exhibit the two-dimensional (2D) network architecture built by [Cu(L1)2]2{[Cu(L2)][Cu(L2)(H2O)]Nb6O19} units and [Cu(L1)2]2+ bridges. 1−3 represent the first 2D architecture with (4,4)-connected topology in polyoxoniobate chemistry. Furthermore, the photoluminescent properties of 1 and 2 have been studied. The magnetic behavior of 1 has been quantitatively investigated and suggests the weak antiferromagnetic exchange interactions.
06/2010;
