ABSTRACT
A series of new trigonal pyramidal {SeO2(OH)} bridging lanthanide-containing antimono-seleno-tungstates [H2N(CH3)2]8Na8Cs4H9[Ln2SeW4O11(OH)(H2O)4(SbW9O33)(SeW9O33)(Se1/2Sb1/2W9O33)]2·32H2O [Ln = Tb (1), Dy (2), Ho (3), Er (4)] have been prepared by the synthetic strategy of simultaneously using the antimonotungstate precursor and simple material in an acidic aqueous solution and structurally characterized by single-crystal X-ray diffraction, powder X-ray diffraction, IR spectrometry, and thermogravimetric analysis. Their molecular structures contain an unprecedented hexameric polyoxoanion [Ln2SeW4O11(OH)(H2O)4(SbW9O33)(SeW9O33)(Se1/2Sb1/2W9O33)]229- constituted by two equivalent trimeric subunits Ln2W4O9(H2O)4(SbW9O33)(SeW9O33)(Se1/2Sb1/2W9O33) bridged via two µ2-{SeO2(OH)} linkers. Furthermore, the catalytic oxidation of various aromatic sulfides and sulfur mustard simulant 2-chloroethyl ethyl sulfide (CEES) by compound 3 as the heterogeneous catalyst has been investigated, exhibiting high conversion and selectivity as well as good stability and recyclability.
ABSTRACT
A new high-nuclear Ti-oxo-cluster-added poly(polyoxometalate) Cs2Na19H12[(Cs@Ti12O18)@{(A-α-SiW9O34) (P2W15O56)3}]·29H2O (1) has been made by reacting two types of trivacant precursors with TiOSO4 under hydrothermal conditions. The polyoxoanion of 1 contains one Keggin-type [A-α-SiW9O34]10- and three Dawson-type [P2W15O56]12- fragments that synergistically induce the Ti4+ ions to aggregate at vacant sites, resulting in a large {Ti12}-oxo-cluster cavity sealing a Cs+ ion. It is worth noting that the {Ti12} cluster is built by three edge-shared Ti3O13 ({Ti3}1) cores and one corner-shared Ti3O15 ({Ti3}2) core bridged via 6 µ2-O, which has never been seen before in polyoxometalate chemistry. Significantly, 1 represents the first example of [A-α-SiW9O34]10- and [P2W15O56]12- simultaneously participating in making poly(polyoxometalate).
ABSTRACT
A novel Zr-added trimer, [H2N(CH3)2]10H14[(Zr2P2W16O61)3]·7H2O (1), has been made under hydrothermal conditions, and contains the highest number of Zr centers in known Dawson-type poly(POM)s. A remarkable feature of this study is the first discovery of a new type of divacant [α-5,10-P2W16O60]14- fragment, which assembles with Zr4+ ions to form a cyclic trimer. Furthermore, 1 as a heterogeneous catalyst exhibits high activity for the selective oxidative degradation of a sulfur mustard simulant CEES.
Subject(s)
Mustard Gas , AnionsABSTRACT
A novel high-nuclear Ni-substituted poly(polyoxometalate) [poly(POM)], [H2N(CH3)2]2Na18Cs2H13[(Cs7(H2O)6)@{(PO4)-@(Ni4(OH)3(WO4))3@(B-α-PW9O34)3}2]·30H2O (1), has been successfully developed and structurally characterized. The polyoxoanion of 1 can be viewed as a unique huge sandwich structure made of an unprecedented Cs7(H2O)6 ({Cs7}) cluster core encapsulated by two trimeric [(PO4)@(Ni4(OH)3(WO4))3@(B-α-PW9O34)3]21- subunits, in which the {Cs7} cluster presents an interesting Anderson-like arrangement and is the first example of a classical POM configuration based on the alkali metal cluster in the POM chemistry. The polyoxoanion can also be described as an unusual [(Cs7(H2O)6)@{(PO4)@(Ni4(OH)3(WO4))3}2]19+ cluster packaged by six {PW9} fragments. Furthermore, investigations on the Knoevenagel condensation reaction reveal that 1 has good catalytic activity for the condensation of various aldehydes and malononitrile into corresponding products with excellent yields.
ABSTRACT
Two novel Ti-oxo wheel cluster substituted silicotungstates (STs) [H2N(CH3)2]9H9[Ti6O6(SiW10O37)3]·11H2O (1) and [H2N(CH3)2]16H10[Ti10O11(SiW10O37)2(SiW9O35)2]·14H2O (2) have been made by hydrothermal reactions. The polyoxoanion of 1 is a ring-shaped trimer where a Ti6O6 ({Ti6}) wheel cluster is encapsulated by three divacant [SiW10O37]10- (SiW10O37) fragments. However, 2 is built by two divacant SiW10O37 units and two rare trivacant [SiW9O35]12- (SiW9O35) fragments and further installs an unprecedented Ti10O11 ({Ti10}) double-wheel cluster. To the best of our knowledge, 2 is rare in POM chemistry. Studies on the catalytic oxidation properties reveal that 1 exhibits high catalytic activity toward the oxidation of various sulfides using H2O2 as an oxidant. Furthermore, 1 can be facilely recycled and reused for at least five cycles without obvious loss of catalytic activity.
ABSTRACT
A novel Ti-W-O-cluster-substituted tungstoantimonate (TA), [H2N(CH3)2]3Na4H9[{Ti6W4O18(OH)(H2O)3}(B-α-SbW9O33)3]·20H2O (1), has been made by hydrothermal reactions of trivacant [B-α-SbW9O33]9- units, Ti4+ cations, and WO42- anions in the presence of [H2N(CH3)2]·Cl and structurally characterized. Intriguingly, the polyoxoanion of 1 is constructed from three [B-α-SbW9O33]9- units and a previously unobserved decanuclear heterometallic Ti-W-O cluster [Ti6W4O18(OH)(H2O)3]11+ ({Ti6W4}) that is comprised of an octahedral [Ti6WO6(H2O)3]18+ cluster and an edge-sharing [W3O12(OH)]7- fragment via six W-O-Ti/W linkers. Furthermore, studies on the catalytic oxidation properties reveal that 1 possesses good catalytic activity toward the oxidation reactions of various sulfides and cyclooctene based on the environmentally friendly oxidant H2O2.
ABSTRACT
A novel tetrahedral µ-AsO4-bridging hexadecanuclear Ni-substituted silicotungstate (ST) Na21H10[(AsO4){Ni8(OH)6(H2O)2(CO3)2(A-α-SiW9O34)2}2]·60H2O (1) was made by the reactions of trivacant [A-α-SiW9O34]10- ({SiW9}) units with Ni2+ cations and Na3AsO4·12H2O and characterized by IR spectrometry, elemental analysis, thermogravimetric analysis (TGA), and powder X-ray diffraction (PXRD). 1 contains a novel polyoxoanion [(AsO4){Ni8(OH)6(H2O)2(CO3)2(A-α-SiW9O34)2}2]31- built by four trivacant Keggin [A-α-SiW9O34]10- fragments linked through an unprecedented [(AsO4){Ni8(OH)6(H2O)2(CO3)2}2]9+ cluster, where the tetrahedral AsO4 acts as an exclusively µ2-bridging unit to link multiple Ni centers; such a connection mode appears for the first time in polyoxometalate chemistry. Furthermore, the electrochemical and catalytic oxidation properties of compound 1 have been investigated.
ABSTRACT
Three novel Zr-substituted polyoxotungstate aggregates [H2N(CH3)2]7NaH2[Zr2Sb2O3(A-α-PW9O34)2]·16H2O (1), [H2N(CH3)2]6H12[ZrSb4(OH)O2(A-α-PW8O32)(A-α-PW9O34)]2·33H2O (2), and [H2N(CH3)2]4Na11.5H4.5[Zr4W8Sb4P5O49(OH)5(B-α-SbW9O33)2]·53H2O (3) have been made in hydrothermal reactions of the [B-α-SbW9O33]9- precursor with Zr4+ cations and PO43- anions in the presence of dimethylamine hydrochloride and sodium acetate buffer (pH = 4.8) and structurally characterized. Different pH values induce structural transformation from tungstoantimonate (TA) to tungstophosphate (TP). 1 is a di-Zr-substituted sandwich-type TP, the tetranuclear heterometallic [Zr2Sb2O3]8+ entity sandwiched by two [A-α-PW9O34]9- moieties. 2 is a double sandwich-type structure, which can be perceived as two equivalent sandwiched [Sb3(PW8O32)(PW9O34)]11- further sandwiching one [Sb2Zr2(OH)2O4]4+ core to form a novel large-size sandwich-type architecture. Different from 1 and 2, 3 is a tetra-Zr-substituted sandwiched configuration, in which two [B-α-SbW9O33]9- fragments sandwich a unique 21-core Sb-P-W-Zr oxo cluster ({Zr4W8Sb4P5}). Furthermore, the catalytic oxidation of aromatic thioethers by 3 as the heterogeneous catalyst has been investigated, showing high conversion and remarkable selectivity as well as excellent recyclability.
ABSTRACT
A new nonanuclear heterometal five-layer sandwich silicotungstate [H2N(CH3)2]6H5NaK{[NaMn8O6(OAc)6][A-α-SiW9O34]2}·34H2O (1) has been made under hydrothermal reactions of MnCl2·4H2O, KMnO4, trivacant [A-α-SiW9O34]10- {SiW9} fragment, and [H2N(CH3)2]·Cl in NaOAc-HOAc buffer (pH = 4.8). The polyoxoanion of 1 is a sandwich architecture, in which the nonanuclear heterometal cluster [NaMn8O6(OAc)6]7+ made of two triangular pyramid clusters [Mn4O3(OAc)3]3+ {Mn4} via a hexacoordinate antitrigonal prism Na+ linkage is encapsulated by two trivacant fragments of {SiW9}. Furthermore, magnetic measurements of compound 1 reveal the existence of antiferromagnetic exchange interactions between the metal centers.
ABSTRACT
A novel octa-Mn-substituted silicotungstate (ST) [H2N(CH3)2]8H19Na4{[K(H2O)4WO4][SiMnW10O38]3}[SiMnW10O38]·27H2O (1) has been made by the hydrothermal reaction of the trivacant [A-α-SiW9O34]10- ({SiW9}) building block with Mn2+ and Mn7+ cations in the presence of dimethylamine hydrochloride and systematically characterized by IR spectroscopy, elemental analysis, thermogravimetric analysis (TGA), powder X-ray diffraction (PXRD) and single crystal X-ray diffraction. 1 is a tetrameric cluster formed by a hexa-MnII substituted cyclic trimeric {[K(H2O)4WO4][SiMnW10O38]3} unit and a {SiMnW10O38} fragment via two W-O-MnIII linkers. Furthermore, its electrochemistry, thermal stability and magnetic properties have been studied.
ABSTRACT
Two multi-Ce3+-substituted selenotungstates (STs), [HDMEA][H2N(CH3)2]4H3Na4[Ce2(H2O)6(DMEA)W4O9(α-SeW9O33)3]·26H2O (1) and [H2N(CH3)2]10H4Na10[Ce2W4O9(H2O)7(α-SeW9O33)3]2·63H2O (2), were prepared by the one-pot approach of sodium tungstate, sodium selenite, and lanthanide nitrate in an acidic water solution in the presence of N, N-dimethylethanolamine (DMEA) or dimethylamine hydrochloride (DMAHC). 1 was obained in the presence of DMEA, whereas 2 was synthesized in the presence of DMAHC. The trimeric polyoxoanion of 1 contains an unusual V-shaped [Se3W29O103]20- group embracing a prominent heterometal oxide fragment, [Ce2(H2O)6(DMEA)W2O5]8+, and the hexameric polyoxoanion of 2 is constructed from two equivalent trimeric [Ce2W4O9(H2O)7(SeW9O33)3]224- subunits through two -O-W-O-Ce-O- linkages. The most worthy of attention is that the polyoxoanion of 1 can be approximatively viewed as a half of the polyoxoanion of 2 because of the coordination and blocking effect of DMEA. The stability of 1 and 2 in different water pH values was studied by electrospray ionization mass spectroscopy (ESI-MS), and the results manifest that 1 and 2 are stable in pH = 3.5-7.5 and 3.5-7.0, respectively. The oxidation reactions of aromatic sulfides catalyzed by H2O2 were studied when 1 or 2 worked as a catalyst, and experimental results reveal that 1 or 2 can serve as available catalysts for the oxidation of aromatic sulfides under mild conditions.
ABSTRACT
Under hydrothermal conditions, three new acetate-functionalized zirconium-substituted polyoxometalates, H4Na2[Na6(H2O)22][Zr4(µ3-O)2(OH)2(OAc)2(α-GeW10O37)2]·32H2O (1), H8K3Na5[Zr6(µ3-O)3(OH)3(OAc)(H2O)(ß-GeW10O37)3]·20H2O (2), H6K4Na12[{Zr5(µ3-OH)4(OH)2}@{Zr2(OAc)2(α-GeW10O38)2}2]·22H2O (3), were synthesized and characterized. In 1, the sandwiched dimer [Zr4(µ3-O)2(OH)2(OAc)2(α-GeW10O37)2]12- was linked to a hexameric [Na6(H2O)22]6+ cluster to form a 1D chain. In 2, the trimer was constructed from three [ß2-GeW10O37]10- units and a new [Zr6O3(OH)3(OAc)(H2O)]14+ cluster. In 3, the tetramer was built by two novel sandwich-type dimers [Zr2(OAc)2(α2-GeW10O38)2]18- and one unique [Zr5(µ3-OH)4(OH)2]14+ core in an approximately orthogonal fashion, showing a staggered tetrahedral polyanion. Also, the electrochemistry and electrocatalytic properties of 3 were studied, exhibiting good catalytic activities toward the reduction of H2O2, BrO3-, and NO2-.
ABSTRACT
A new tetra-Zr-substituted tungstophosphate (TP), [H2N(CH3)2]6Na6H8{Zr2[SbP2W4(OH)2O21][α2-PW10O38]}2·50H2O (1), has been made by the hydrothermal reaction of the [B-α-SbW9O33]9- building block with Zr4+ cations and PO43- anions in the presence of dimethylamine hydrochloride and NaOAc-HOAc (pH = 4.8), and further characterized by IR spectroscopy, elemental analysis, thermogravimetric analysis (TGA), powder X-ray diffraction (PXRD), 31P NMR spectroscopy and single-crystal X-ray diffraction. 1 is a toroidal structure formed by two divacant [α2-PW10O38]11- units and two [SbP2W4(OH)2O21]7- fragments linked by four Zr4+ cations. Note that the TP is reassembled with tetrahedral PO4 replacing the triangular pyramidal SbO3 in the [B-α-SbW9O33]9- precursor. In addition, the pendant SbO3 derives from the dissociation of the [B-α-SbW9O33]9- precursor. Furthermore, the electrochemical properties of 1 have been studied in Na2SO4 + H2SO4 supporting electrolyte (0.5 mol L-1), and indicate that 1 exhibits apparent catalytic activity toward H2O2 and BrO3- reduction. The 31P NMR spectrum of 1 exhibits three signals with approximately proportional intensities, which is consistent with the solid-state structure.
ABSTRACT
In the presence of the larger [H2 N(CH3 )2 ]+ and K+ counter cations as structure-stabilizing agents, a class of unprecedented selenium and lanthanide (Ln) simultaneously bridging tetra-vacant Dawson-like selenotungstate aggregates [H2 N(CH3 )2 ]2 Na9 K2 H19 {[Ln4 W4 Se4 O22 (H2 O)5 ](Se2 W14 O52 )2 }2 â 60 H2 O [Ln=TbIII (1), DyIII (2), HoIII (3), ErIII (4), TmIII (5), YbIII (6)] have been obtained by the one-pot assembly reaction of Na2 WO4 â 2 H2 O, Ln(NO3 )3 â 6 H2 O, and Na2 SeO3 under moderately acidic aqueous conditions and the complexes were structurally characterized by elemental analyses, IR spectra, single-crystal X-ray diffraction, powder X-ray diffraction (PXRD), and thermogravimetric (TG) analyses. It should be noted that the appropriate molar ratio of Se/W is extremely important in the formation of 1-6 and can effectively ameliorate the yield of 1-6. Moreover, dimethylamine hydrochloride is also indispensable and plays a considerably important role in improving the solubility of Ln ions and stabilizing the structures of 1-6. The main polyoxoanion skeletons of 1-6 are constructed from two sandwich-type tetra-vacant Dawson-like {[Ln4 W4 Se4 O22 (H2 O)5 ](Se2 W14 O52 )2 }16- half-units linked through two W-O-Ln bridges. The sandwich-type half-unit comprises two tetra-vacant Dawson-like [Se2 W14 O52 ]12- fragments encapsulating a unique dodecanuclear Se-Ln-W [Ln4 W4 Se4 O22 (H2 O)5 ]8+ oxo cluster. Their solid-state visible and NIR fluorescent properties and lifetime decay behaviors were measured and their solid-state luminescent spectra mainly demonstrate the characteristic emission bands of Ln3+ ions. Moreover, the dominant wavelengths, the color purity, and correlated color temperatures of 1-5 have been also calculated. In addition, the luminous flux values of 1-5 are 2031, 6992, 3071, 921, and 477â lumen, respectively.
ABSTRACT
Three types of serine-decorated rare- earth-containing arsenotungstate [H2 N(CH3 )2 ]6 NaH[RE2 W4 O10 (H2 O)8 (Ser)2 (B-α-AsW9 O33 )2 ]â 30 H2 O (RE3+ =Eu3+ , Gd3+ , Tb3+ , Dy3+ , Ho3+ , Er3+ , Tm3+ , Yb3+ , and Y3+ ; 1), [H2 N(CH3 )2 ]6 Na6-x REx H4-2 x [RE4 W8 O19 (H2 O)10+y (OH)2 (Ser)2 (B-α-AsW9 O33 )4 ]â n H2 O (RE3+ =Tb3+ , x=1, y=2, n=36; RE3+ =Dy3+ , Ho3+ , Er3+ , Yb3+ , Y3+ , x=0, y=0, n=38; RE3+ = Tm3+ , x=1, y=0, n=38; Ser=serine; 2), and [H2 N(CH3 )2 ]6-2 x Na2+3 x REx H10-6 x+y [RE4 W8 O19 (H2 O)8 (OH)2 (Ser)4 (B-α-AsW9 O33 )4 ]â Cly â n H2 O (RE3+ =Ce3+ , Pr3+ , x=1, y=0, n=65; RE3+ =Nd3+ , Sm3+ , x=0, y=0, n=65; RE3+ =Eu3+ , Gd3+ , x=1, y=2, n=45; 3) were synthesized with the participation of the organic solubilizers dimethylamine hydrochloride and l-serine and were structurally characterized. The use of different amounts of rare-earth salts results in the structural transformation from dimerization to tetramerization of types 1-3. Type 1 is a dimeric sandwich-type assembly of a dual-Ser-participating [RE2 W4 O10 (H2 O)8 (Ser)2 ]10+ entity sandwiched by two [B-α-AsW9 O33 ]9- moieties, whereas types 2 and 3 have a tetrameric square structure formed by four [B-α-AsW9 O33 ]9- moieties that anchor a dual/tetra- Ser-participating [RE4 W8 O19 (H2 O)10+y (OH)2 (Ser)2 ]20+ or [RE4 W8 O19 (H2 O)8 (OH)2 (Ser)4 ]20+ core. The solid-state luminescence properties and lifetime-decay behaviors of these compounds were investigated. The chromaticity coordinates, dominant wavelengths, color purities, and correlated color temperatures were also calculated.
ABSTRACT
By virtue of the stereochemical effect of the lone-electron pair located on the trigonal-pyramidal-AsO3 groups and the one-pot self-assembly strategy in the conventional aqueous solution, a series of novel lanthanide-bridging and lone-electron-pair active trigonal-pyramidal-AsO3 inducing nanosized poly(polyoxotungstate) aggregates [H2N(CH3)2]6 Na24H16{[Ln10W16(H2O)30O50](B-α-AsW9O33)8}·97H2O [Ln = Eu(III) (1), Sm(III) (2), Gd(III) (3), Tb(III) (4), Dy(III) (5), Ho(III) (6), Er(III) (7), Tm(III) (8)] were prepared and further characterized by elemental analyses, IR spectra, UV spectra, thermogravimetric (TG) analyses and single-crystal X-ray diffraction. The most remarkable structural feature is that the polyanionic skeleton of {[Ln10W16(H2O)30O50](B-α-AsW9O33)8}(46-) is constructed from eight trivacant Keggin [B-α-AsW9O33](9-) fragments through ten Ln centers and sixteen bridging W atoms in the participation of fifty extraneous oxygen atoms. Notably, 4 and 8 can be stable in the aqueous solution not only for eight days but also in the range of pH = 3.9-7.5. Moreover, the cytotoxicity tests of 4 and 8 toward human cervical cancer (HeLa) cells, human breast cancer (MCF-7) cells and mouse fibroblast (L929) cells were performed by the 3-(4,5-cimethylthiazol-2-yl)-2,5-diphenyl tetrazolium bromide (MTT) assay and the cell apoptosis processes were characterized by calcein AM/PI staining experiments, annexin V-FITC/PI staining experiments and morphological changes.