Co-reporter:Jiangli Meng;Jiaqi Fu;Xiaoxuan Yang;Meijie Wei;Song Liang;Hong-Ying Zang;Huaqiao Tan;Yonghui Wang;Yangguang Li
Inorganic Chemistry Frontiers 2017 vol. 4(Issue 11) pp:1791-1797
Publication Date(Web):2017/11/07
DOI:10.1039/C7QI00435D
The development of stable, highly active and cheap electrocatalysts towards the oxygen evolution reaction (OER) has been an ongoing challenge due to practical problems such as slow kinetics and high overpotential. Herein, we utilized a one-pot hydrothermal method to prepare cobalt/nickel molybdate hierarchical microflowers on conductive carbon cloth (MMoO4-CC, M = Co, Ni) as three-dimensional self-supported electrodes for the oxygen evolution reaction. CoMoO4-CC showed better catalytic activity than NiMoO4-CC. Benefiting from the synergistic effect of a large active area, fast charge and mass transport as well as a three-dimensional conducting path, the CoMoO4-CC nanosheet electrode showed a large current density and a relatively low starting potential, delivering 10 mA cm−2 current densities at an overpotential of 290 mV and a Tafel slope of 94 mV dec−1. Furthermore, the CoMoO4-CC nanomaterial shows better electrocatalytic stability than IrO2-CCa, which could be a promising electrocatalyst for large-scale water oxidation.
Co-reporter:Gang Yan;Xiaojia Feng;Liguang Xiao;Wenguang Xi;Huaqiao Tan;Hongfei Shi;Yonghui Wang;Yangguang Li
Dalton Transactions 2017 vol. 46(Issue 46) pp:16019-16024
Publication Date(Web):2017/11/28
DOI:10.1039/C7DT03372A
Carbon nitride (g-C3N4), as a rising star of metal-free photocatalysts, has received considerable attention. However, for practical application, the photocatalytic efficiency of g-C3N4 remains to be further improved. Herein, a series of Keggin-type polyoxoanion (polyoxoanions = SiW12O404−, PW12O403−, PMo12O403−) modified g-C3N4 (POM/C3N4) composites have been successfully prepared. The results of XRD, TEM, XPS and EDAX reveal that a small amount of polyoxoanions was modified on the surface of g-C3N4 with electrostatic and hydrogen bonding interactions. Photocatalytic experiments indicate that these composites exhibit enhanced methyl orange (MO) degradation photocatalytic activity and water splitting H2 production under visible light irradiation. The loading amount and the type of polyoxoanion can tune the photocatalytic performance of the composites. Among these catalysts, 5% SiW12O404− (SiW12)-modified g-C3N4 has the best photocatalytic performance, which is 4.4 times higher than that of pure g-C3N4 for the degradation of MO. The photocatalytic mechanism reveals that polyoxoanions can act as electron traps, which can efficiently promote the separation of photogenerated electrons and holes of C3N4, thus resulting in the enhanced photocatalytic performance of the composites.
Co-reporter:Lu-Lu Li, Hua-Yan Han, Yong-Hui Wang, Hua-Qiao Tan, Hong-Ying Zang and Yang-Guang Li
Dalton Transactions 2015 vol. 44(Issue 25) pp:11429-11436
Publication Date(Web):29 May 2015
DOI:10.1039/C5DT00686D
A series of polynuclear metal-oxo clusters have been constructed from the dynamic polyoxometalate (POM) building block {B-α-SbIIIW9O33} and lanthanide (Ln) linkers via a stepwise synthetic strategy with the molecular formulas of [Ln2(H2O)4{WO2(pic)}2(SbW8O30)2]10− (Na4Li6[La-1]·28H2O, Na3Li7[Pr-2]·30H2O) and [{Ln(H2O)}{Ln(pic)}(Sb3O4)(SbW8O31)(SbW10O35)]224− (K2Na6Li16[Tb-3]·63H2O, Na9Li15[Dy-4]·61H2O, Na7Li17[Ho-5]·53H2O) (Hpic = picolinic acid). The five compounds have been characterized by FT-IR, elemental analysis, TG, powder X-ray diffraction (PXRD) and single crystal X-ray diffraction. In compounds 1–5, various POM moieties, such as {B-β-SbW8O30}, {B-α-SbW8O31} and {B-α-SbW10O35}, were formed through a series of disassembling and re-assembling processes of the dynamic {B-α-SbW9O33} precursor with specific pH, reaction temperature and time. Furthermore, the use of oxytropic Ln3+ ions as linkers, together with auxiliary organic pic ligands and/or inorganic Sb3+ ions, led to diverse connection modes between the POM building blocks and Ln linkers and the assembly of new polynuclear metal-oxo clusters. The polyoxoanions of La-1 and Pr-2 possess the same structural feature, which can be viewed as a sandwich-type cluster composed of two {B-β-SbW8O30} units connected by two {WO2(pic)} fragments and two hydrated Ln ions. These sandwich-type polyoxoanions are further linked by the hydrated Ln ions to form a 1-D helical chain. The polyoxoanions of Tb-3, Dy-4 and Ho-5 display the same structural features, although they contain different counter-cations and lattice water molecules. In the polyoxoanions of 3–5, one {B-α-SbW8O31} POM moiety and one {B-α-SbW10O35} POM unit are connected by one {Sb3O4} fragment and one {Ln(pic)} linker, forming an asymmetric sandwich-type metal-oxo cluster. Two of these sandwich-type clusters are further fused together by extra two hydrated Ln ions, leading to an isolated polynuclear metal-oxo cluster with a size of 16.4 × 28.5 Å. The photoluminescence properties of Tb-3 and Dy-4 were investigated. Both compounds exhibit characteristic Tb3+ and Dy3+ luminescence. The relationship between the luminescence properties and the crystal structure of the polyoxoanion was discussed.
Co-reporter:Xiu-Li Hao, Yuan-Yuan Ma, Yong-Hui Wang, Wen-Zhe Zhou, Yang-Guang Li
Inorganic Chemistry Communications 2014 Volume 41() pp:19-24
Publication Date(Web):March 2014
DOI:10.1016/j.inoche.2013.12.032
•New assemblies based on metal-bis(betaine) and POM units were synthesized.•The assemblies can be tuned by changing the cationic species.•Both compounds show good UV photocatalytic activity for RhB degradation.The slow diffusion reactions of a double-betaine-containing ligand with YbH[SiMo12O40]·nH2O and Ca2[SiMo12O40]·nH2O led to the isolation of two new organic–inorganic hybrid assemblies, [Yb(O)(HL)2(H2L)0.5(H2O)3][SiMo12O40]·2.5CH3CN·1.5H2O (1) and [Ca(HL)2(L)0.5(H2O)4] [SiMo12O40]·5CH3CN·H2O (2) (L = 1,4-bis(pyridinil-4-carboxylato)-l,4-dimethylbenzene). Compounds 1–2 were characterized by elemental analyses, TG, IR, XPS and single-crystal X-ray diffraction. Compound 1 contains the dinuclear [(YbO)(HL)2(H2O)3]2 coordination moieties and discrete protonated L ligands, which are connected together by H-bonds and π–π interactions to form a 3D supramolecular framework with the Keggin-type [SiMo12O40]4 − polyoxoanions and solvent molecules encapsulated. Compound 2 possesses discrete [Ca(HL)2(L)0.5(H2O)4]2 coordination units that are linked by the extensive intermolecular H-bonds and π–π interactions to form a 3D supramolecular framework with the [SiMo12O40]4 − polyoxoanions and solvent molecules are encapsulated in the interbedded cavities. The structural motifs of the metal–organic coordination units can be obviously modulated by the use of chemically different cationic nodes. The degradation of Rhodamine-B (RhB) under UV irradiation with compounds 1 and 2 as heterogeneous photocatalysts were investigated, both exhibiting good photocatalytic properties. Furthermore, these hybrid compounds display luminescent properties induced by organic ligands.New organic–inorganic hybrid supramolecular frameworks based on metal–bis(betaine) coordination moieties and Keggin-type polyoxometalates (POMs) were assembled by changing metal cations.
Co-reporter:Xiu-Li Hao;Yuan-Yuan Ma;Dr. Yong-Hui Wang;Long-Yang Xu;Dr. Fu-Chen Liu;Mao-Mao Zhang; Yang-Guang Li
Chemistry – An Asian Journal 2014 Volume 9( Issue 3) pp:819-829
Publication Date(Web):
DOI:10.1002/asia.201301378
Abstract
Investigation into a hydrothermal reaction system with transition-metal (TM) ions, 1,4-bis(1,2,4-triazol-1-lmethyl)benzene (BBTZ) and various charge-tunable Keggin-type polyoxometalates (POMs) led to the preparation of four new entangled coordination networks, [CoII(HBBTZ)(BBTZ)2.5][PMo12O40] (1), [CuI(BBTZ)]5[BW12O40]⋅H2O (2), [CuII(BBTZ)]3[AsWV3WVI9O40]⋅10 H2O (3), and [CuII5(BBTZ)7(H2O)6][P2W22Cu2O77(OH)2]⋅6 H2O (4). All compounds were characterized by using elemental analysis, IR spectroscopy, thermogravimetric analysis, powder X-ray diffraction, and single-crystal X-ray diffraction. The mixed valence of W centers in compound 3 was further confirmed by using XPS spectroscopy and bond-valence sum calculations. In the structural analysis, the entangled networks of 1–4 demonstrate zipper-closing packing, 3D polythreading, 3D polycatenation, and 3D self-penetration, respectively. Moreover, with the enhancement of POM negative charges and the use of different TM types, the number of nodes in the coordination networks of 1–4 increased and the basic metal–organic building motifs changed from a 1D zipper-type chain (in 1) to a 2D pseudorotaxane layer (in 2) to a 3D diamond-like framework (in 3) and finally to a 3D self-penetrating framework (in 4). The photocatalytic properties of compounds 1–4 for the degradation of methylene blue under UV light were also investigated; all compounds showed good catalytic activity and the photocatalytic activity order of Keggin-type species was initially found to be {XMo12O40}>{XW12O40}>{XW12−nTMnO40}.
Co-reporter:Xiu-Li Hao;Yuan-Yuan Ma;Dr. Yong-Hui Wang;Long-Yang Xu;Dr. Fu-Chen Liu;Mao-Mao Zhang; Yang-Guang Li
Chemistry – An Asian Journal 2014 Volume 9( Issue 3) pp:
Publication Date(Web):
DOI:10.1002/asia.201490004
Co-reporter:Xiao-Jia Feng, Hua-Yan Han, Yong-Hui Wang, Lu-Lu Li, Yang-Guang Li and En-Bo Wang
CrystEngComm 2013 vol. 15(Issue 36) pp:7267-7273
Publication Date(Web):11 Jul 2013
DOI:10.1039/C3CE40686E
A series of new chainlike polyoxometalate(POM)-based lanthanide (Ln) complexes, Na10[Ln6(H2O)x{As4W44(OH)2(proline)2O151}]·nH2O (Ln = Tb(III), x = 22 and n = 22 for 1; Ln = Dy(III), x = 22 and n = 25 for 2; Ln = Nd(III), x = 26 and n = 31 for 3) were isolated from a one-pot reaction system. In such a reaction system, the initial three discrete solutions, namely K14[As2W19O67(H2O)] precursor in solution A, Ln3+ ion and proline in solution B, and NaCl in solution C, were simultaneously mixed together in one-pot reaction field with pH = 1.5 and heated at 80 °C for 1.5 h, leading to the isolation of crystalline compounds 1–3. The crystal structure of 1–3 contains a crown-type POM-based cluster embedded with four hydrated Ln(III) ions. Moreover, these clusters were further linked by extra two hydrate Ln(III) ions into one-dimensional chains. Photoluminescent properties of compounds 1–3 were also investigated, exhibiting the characteristic emission peaks of relevant Ln(III) ions.
Co-reporter:Xin Wang, Mao-Mao Zhang, Xiu-Li Hao, Yong-Hui Wang, Ying Wei, Fu-Shun Liang, Li-Jie Xu, and Yang-Guang Li
Crystal Growth & Design 2013 Volume 13(Issue 8) pp:3454-3462
Publication Date(Web):July 3, 2013
DOI:10.1021/cg400353j
The introduction of polyoxometalates (POMs) into the metal–organic complex synthetic system containing copper ions and bichelate-bridging ligands (bis(3-(2-pyridyl)pyrazole-1-ylmethyl)benzene, bppmb) led to the isolation of three new organic–inorganic hybrid compounds [CuIILo]2H[BW12O40]·4H2O (1), [CuILo]4[SiW12O40]·5H2O (2), and [CuLp]3H2[BW12O40]·5H2O (3) (Lo = 1,2-bppmb and Lp = 1,4-bppmb). All three compounds were hydrothermally synthesized and characterized by elemental analyses, IR spectra, TG analyses, powder X-ray diffraction, and single-crystal X-ray diffraction analyses. In these compounds, the use of Keggin-type POMs induces the formation of a series of new metal–organic secondary building units based on the copper ions and bppmb ligands such as helical chain and chiral Möbius Strip, which further form interesting supramolecular self-assemblies with the polyoxoanions. The degradation of Rhodamine-B (RhB) under UV irradiation with compounds 1–3 as the heterogeneous photocatalysts was investigated, and these compounds show good photocatalytic properties for RhB degradation.
Co-reporter:Dan Li;Huayan Han;Yonghui Wang;Xin Wang;Yangguang Li ;Enbo Wang
European Journal of Inorganic Chemistry 2013 Volume 2013( Issue 10-11) pp:1926-1934
Publication Date(Web):
DOI:10.1002/ejic.201200791
Abstract
The introduction of hydrogen peroxide, dl-mandelic acid (H2Mal), and acetate buffer into a reaction system containing zirconium(IV) ions and various trivacant polyoxometalates (POMs) led to the isolation of a series of new tetranuclear zirconium-substituted POMs modified by different O-donor ligands: Na4(NH4)14[Zr4(μ3-O)2(μ-O2)2(OAc)2(P2W16O59)2]·51H2O (1), (NH4)16[Zr4(μ3-O)2(Mal)2(H2O)2(P2W16O59)2]·14H2O (2), and Na7(NH4)5[{Zr4(OH)6(OAc)2}(SiW10O37)2]·20H2O(3) (3). All three compounds were characterized by elemental analyses, IR spectra, thermogravimetric (TG) analysis and single-crystal X-ray diffraction structural analyses. Compounds 1 and 2 possess similar sandwich-type polyoxoanion structures built from a tetranuclear Zr cluster and two [P2W16O59]12– building blocks, but they differ in the modifying ligands on the {Zr4} clusters, which are peroxido and mandelato for 1 and 2, respectively. The polyoxoanion of 3 contains a different tetranuclear Zr cluster, which is further sandwiched by two [α-SiW10O37]10– moieties and decorated by two acetato ligands. The catalytic activities of 1–3 were evaluated on the basis of a catalytic oxidation reaction of the peroxidase substrate 3,3′,5,5′-tetramethylbenzidine (TMB) by H2O2. Compound 1 exhibits the best catalytic activity, which suggests a new peroxidase-like catalyst for the colorimetric detection of H2O2 with a linear detection range from 100 to 1000 μM (r = 0.997) and a detection limit of 100 μM.
Co-reporter:Gang Yan, Xin Wang, Yuanyuan Ma, Xin Cheng, Yonghui Wang, Yangguang Li
Solid State Sciences 2013 Volume 17() pp:146-150
Publication Date(Web):March 2013
DOI:10.1016/j.solidstatesciences.2012.11.018
A new paratungstate-A-based organic–inorganic hybrid compound with the chemical formula of [Co(en)3]2[H2W7O24]·8H2O (en = ethylenediamine) (1) has been hydrothermally synthesized and structurally characterized by the elemental analysis, IR, TG, powder X-ray diffraction (PXRD) and single-crystal X-ray diffraction. Compound 1 crystallizes in the monoclinic space group P21/c with a = 17.216(3) Å, b = 14.986(3) Å, c = 23.088(8) Å, β = 128.151(2)°, V = 4684.2 Å3, Z = 1, R1 = 0.0484, and wR2 = 0.1087. The structure of 1 consists of the [H2W7O24]4− building blocks and [Co(en)3]2+ metal-organic cationic moieties, which are packed together via the electrostatic forces and extensive hydrogen-bonding interactions to form a three-dimensional supramolecular framework. Interestingly, compound 1 represents the first structurally-defined hybrid compound based on the metastable paratungstate-A polyoxoanions and metal–organic units. The degradation of Rhodamine-B (RhB) under UV irradiation with 1 as the heterogeneous photocatalyst has been investigated, showing a good photocatalytic property of 1 for RhB degradation.A new paratungstate-A-based hybrid compound was hydrothermally synthesized, exhibiting efficient photocatalytic property for the degradation of Rhodamine-B under UV irradiation.
Co-reporter:Xiu-Li Hao, Yuan-Yuan Ma, Chen Zhang, Qian Wang, Xin Cheng, Yong-Hui Wang, Yang-Guang Li and En-Bo Wang
CrystEngComm 2012 vol. 14(Issue 20) pp:6573-6580
Publication Date(Web):06 Jul 2012
DOI:10.1039/C2CE25747E
Three new organic–inorganic hybrid compounds based on copper-bis(triazole) complexes and Keggin-type polyoxometalates (POMs) with different negative charges, [Cu(I)BBTZ]3[PMo12O40] (1), [Cu(I)BBTZ][Cu(I)(HBBTZ)2][SiMo12O40]·2.5H2O (2) and [Cu(I)BBTZ]6[SiWV2WVI10O40]·2H2O (3) (BBTZ = 1,4-bis(1,2,4-triazol-1-ylmethyl)benzene), have been hydrothermally prepared and characterized by elemental analyses, IR spectra, TG analyses, XPS spectra, powder X-ray diffraction and single-crystal X-ray diffraction analyses. Compounds 1 and 2 exhibit the POM-templated 3D host–guest supramolecular frameworks. Compound 3 displays a POM-supported 3D open framework. In these three hybrid compounds, the structural transformation from host–guest framework to open framework were modulated by the introduction of Keggin-type polyoxoanions with different negative charges. Moreover, the electrochemical properties of compounds 1–3 were investigated and all these compounds show the electrocatalytic activities towards the reduction of nitrite.
Co-reporter:Xiu-Li Hao, Ming-Fa Luo, Xin Wang, Xiao-Jia Feng, Yang-Guang Li, Yong-Hui Wang, En-Bo Wang
Inorganic Chemistry Communications 2011 Volume 14(Issue 11) pp:1698-1702
Publication Date(Web):November 2011
DOI:10.1016/j.inoche.2011.06.035
The reaction between a double-betaine-containing ligand and DyH[PMo11VO40]·nH2O led to a new polyoxometalate-based lanthanide-organic hybrid compound with the molecular formula [Dy(HL)(L)1.5(H2O)3][PMo11VO40]·8H2O (1) (L = 1,4-bis(pyridinil-4-carboxylato)-l,4-dimethylbenzene). Compound 1 was characterized by elemental analyses, TG, IR, XPS and the single-crystal X-ray diffraction. Compound 1 possesses a cationic 1D polymeric chain [Dy(HL)(L)1.5(H2O)3]n4n+ with cyclic-, chain- and semi-cyclic-like fragments, corresponding to three different configurations of the double-betaine-containing ligand. These 1D chains are connected together by the H-bonds and π–π interactions to form a 3D supramolecular framework, encapsulating the vanadium-substituted Keggin-type polyoxoanions [PMo11VO40]4−and the solvent molecules. This composite compound displays electrocatalytic activities towards the reduction of nitrite and the luminescent property.The reaction between a double-betaine-containing ligand and LnHPMo11VO40·nH2O leads to a new polyoxometalate-based lanthanide-organic hybrid chain.Highlights► In this study we report a new polyoxometalate(POM)-based lanthanide-organic hybrid compound. ► The exchange of POMs can tune the structure of the lanthanide-organic coordination fragments. ► Interestingly, the betaine-containing ligands in 1 exhibit three different configurations. ► Compound 1 displays both luminescent and electrocatalytic activities.
Co-reporter:Yun-Wu Li, Yang-Guang Li, Yong-Hui Wang, Xiao-Jia Feng, Ying Lu and En-Bo Wang
Inorganic Chemistry 2009 Volume 48(Issue 14) pp:6452-6458
Publication Date(Web):June 18, 2009
DOI:10.1021/ic9001362
The introduction of hexavacant Dawson-type precursor K12[H2P2W12O48]·24H2O into a HOAc/NaOAc (OAc− = acetate) buffer system containing (NH4)2[CeIV(NO3)6] and MnII(OAc)2·4H2O led to the isolation of a new compound, Na20[CeIV3MnIV2O6(OAc)6(H2O)9]2[MnIII2P2W16O60]3·21H2O (1). Compound 1 contains unusual triple-Dawson-type polyoxoanions [MnIII2P2W16O60]324− and bipyramid-like 3d−4f heterometallic clusters [CeIV3MnIV2O6(OAc)6(H2O)9]2+, which are arranged in a 3-D supramolecular assembly with 1-D channels. The Na+ cations and solvent water molecules reside in the channels. Crystal data for 1 are as follows: hexagonal, P63/mcm (No. 193), a = 24.959(4) Å, c = 26.923(5) Å, γ = 120°, V = 14525(4) Å3, and Z = 2. The electrochemical and electrocatalytic properties of compound 1 have been investigated.
Co-reporter:Yun-Wu Li, Yong-Hui Wang, Yang-Guang Li, En-Bo Wang, Wei-Lin Chen, Qiong Wu, Quan Shi
Inorganica Chimica Acta 2009 Volume 362(Issue 4) pp:1078-1082
Publication Date(Web):2 March 2009
DOI:10.1016/j.ica.2008.05.021
The hydrothermal reaction of [H2W12O42]10− precursors and CuCl2 in a CH3COOK/CH3COOH solution (pH 3.5) led to the isolation of a new compound, KNa3[Cu(H2O)2{Cu(H2O)3}2(H2W12O42)] · 16H2O (1). Compound 1 possesses a new anionic three-dimensional (3-D) open-framework based on the [H2W12O42]10− building blocks and CuII linkers. This anionic 3-D framework represents the first example of a (8,3)-connected structural topology in POM-based solid materials. The magnetic behavior of 1 exhibits weak antiferromagnetic interaction.The hydrothermal synthesis of paradodecatungstate and CuCl2 in an acetate buffer solution led to the isolation of a new compound, KNa3[Cu(H2O)2{Cu(H2O)3}2(H2W12O42)] · 16H2O (1). Compound 1 displays a pure inorganic anionic 3-D open-framework based on [H2W12O42]10− building blocks and CuII linkers. It represents the first example of a (8,3)-connected network in POM-based solid materials from the topological point of view.
Co-reporter:Yunwu Li, Yonghui Wang, Yangguang Li, Enbo Wang
Inorganic Chemistry Communications 2009 Volume 12(Issue 2) pp:112-115
Publication Date(Web):February 2009
DOI:10.1016/j.inoche.2008.11.023
A novel layered supramolecular compound [N(CH3)4]2[Mn(Salen)(DMF)2]2[β-Mo8O26] · 2DMF (1) (H2salen = N,N′-ethylenebis(salicylideneimine)) has been synthesized and characterized by elemental analysis, IR, TG, UV and single-crystal X-ray diffraction analysis. Compound 1 represents a new and rare example constructed by MnIII-salen Schiff-base building blocks and β-octamolybdate isopolyoxoanions. Moreover, the reaction contains the unusual N(CH3)4+ cations generated in situ from the decomposition and alkylation reaction of DMF precursors. The electrochemical of cyclic voltammetry and electrocatalytic properties of 1 have been well investigated.A novel layered supramolecular compound [N(CH3)4]2[Mn(Salen)(DMF)2]2[β-Mo8O26] · 2DMF (1), has been synthesized and structurally characterized. Compound 1 represents a new and rare example constructed by β-octamolybdate isopolyoxoanions and MnIII-salen Schiff-base building blocks. Moreover, the reaction contains the unusual N(CH3)4+ cations generated in situ from the decomposition and alkylation reaction of DMF precursors.
Co-reporter:Lu-Lu Li, Hua-Yan Han, Yong-Hui Wang, Hua-Qiao Tan, Hong-Ying Zang and Yang-Guang Li
Dalton Transactions 2015 - vol. 44(Issue 25) pp:NaN11436-11436
Publication Date(Web):2015/05/29
DOI:10.1039/C5DT00686D
A series of polynuclear metal-oxo clusters have been constructed from the dynamic polyoxometalate (POM) building block {B-α-SbIIIW9O33} and lanthanide (Ln) linkers via a stepwise synthetic strategy with the molecular formulas of [Ln2(H2O)4{WO2(pic)}2(SbW8O30)2]10− (Na4Li6[La-1]·28H2O, Na3Li7[Pr-2]·30H2O) and [{Ln(H2O)}{Ln(pic)}(Sb3O4)(SbW8O31)(SbW10O35)]224− (K2Na6Li16[Tb-3]·63H2O, Na9Li15[Dy-4]·61H2O, Na7Li17[Ho-5]·53H2O) (Hpic = picolinic acid). The five compounds have been characterized by FT-IR, elemental analysis, TG, powder X-ray diffraction (PXRD) and single crystal X-ray diffraction. In compounds 1–5, various POM moieties, such as {B-β-SbW8O30}, {B-α-SbW8O31} and {B-α-SbW10O35}, were formed through a series of disassembling and re-assembling processes of the dynamic {B-α-SbW9O33} precursor with specific pH, reaction temperature and time. Furthermore, the use of oxytropic Ln3+ ions as linkers, together with auxiliary organic pic ligands and/or inorganic Sb3+ ions, led to diverse connection modes between the POM building blocks and Ln linkers and the assembly of new polynuclear metal-oxo clusters. The polyoxoanions of La-1 and Pr-2 possess the same structural feature, which can be viewed as a sandwich-type cluster composed of two {B-β-SbW8O30} units connected by two {WO2(pic)} fragments and two hydrated Ln ions. These sandwich-type polyoxoanions are further linked by the hydrated Ln ions to form a 1-D helical chain. The polyoxoanions of Tb-3, Dy-4 and Ho-5 display the same structural features, although they contain different counter-cations and lattice water molecules. In the polyoxoanions of 3–5, one {B-α-SbW8O31} POM moiety and one {B-α-SbW10O35} POM unit are connected by one {Sb3O4} fragment and one {Ln(pic)} linker, forming an asymmetric sandwich-type metal-oxo cluster. Two of these sandwich-type clusters are further fused together by extra two hydrated Ln ions, leading to an isolated polynuclear metal-oxo cluster with a size of 16.4 × 28.5 Å. The photoluminescence properties of Tb-3 and Dy-4 were investigated. Both compounds exhibit characteristic Tb3+ and Dy3+ luminescence. The relationship between the luminescence properties and the crystal structure of the polyoxoanion was discussed.
![Tungstate(10-), [m9-[orthosilicato(4-)-kO:kO:kO:kO':kO':kO'':kO'':kO''':kO''']]pentadeca-m-oxopentadecaoxonona-, sodium (1:10)](http://img.cochemist.com/ccimg/64700/64684-57-7.png)
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![6-phenyl-7-oxabicyclo[4.1.0]heptane](http://img.cochemist.com/ccimg/4900/4829-01-0_b.png)
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![Tungstate(3-),tetracosa-m-oxododecaoxo[m12-[phosphato(3-)-kO:kO:kO:kO':kO':kO':kO'':kO'':kO'':kO''':kO''':kO''']]dodeca-,hydrogen (1:3)](http://img.cochemist.com/ccimg/1400/1343-93-7_b.png)