Synthesis, Characterization, Electrochemistry, Photoluminescence and Magnetic Properties of a Dinuclear Erbium(III)-Containing Monolacunary Dawson-Type Tungstophosphate: [{Er(HO)(CHCOO)(PWO)}].

Reaction of the trilacunary Wells-Dawson anion {α-PWO} with Er ion in a 1 M LiOAc/HOAc buffer (pH 4.8) solution produces a dinuclear erbium(III) substituted sandwich-type structure [{Er(HO)(CHCOO)(PWO)}] (). The isolated compound was structurally characterized using single crystal and powder X-ray diffraction, FTIR spectroscopy, mass spectrometry and thermogravimetric analysis.

Syntheses, Crystal Structure, Electrocatalytic, and Magnetic Properties of the Monolanthanide-Containing Germanotungstates [Ln(HO) GeWO] (Ln = Dy, Er, = 4,3).

Two monolanthanide-containing polyanions based on monolacunary Keggin germanotungstates [Ln(HO) GeWO] (Ln = Dy, Er, = 4,3) have been synthesized in simple one-pot synthetic procedure and compositionally characterized in solid state by single-crystal X-ray diffraction, powder X-ray diffraction, Fourier transform infrared spectroscopy, thermogravimetric analysis, and elemental analysis. Electronic absorption and emission spectra of the title compounds in solution were also studied. The [Dy(HO)GeWO] Keggin POM exhibits a slow relaxation of magnetization.

Synthesis, structure and electrochemical characterization of an isopolytungstate (WO) held by Mn anchors within a superlacunary crown heteropolyanion {PW}.

An isopolyanion {WO} within an archetypal {PW} heteropolyanion assembly [(PWO)(WO)KLiMnNa(HO)Cl] (MnW-PW) has been synthesized by the reaction of the cyclic superlacunary anion [HPWO] and Mn(ClO)·6HO in 1 M LiCl solution medium at pH 8. The isolated compound has been characterized by single-crystal X-ray crystallography, powder X-ray diffraction (PXRD), Fourier-transform infrared (FTIR) spectroscopy, elemental analysis and thermogravimetric analysis. Electrochemical studies were also performed on MnW-PW, which confirmed the presence of Mn centres bonded to the tungstic framework.

Two New Sandwich-Type Manganese {Mn5}-Substituted Polyoxotungstates: Syntheses, Crystal Structures, Electrochemistry, and Magnetic Properties.

Herein we report two pentanuclear Mn-substituted sandwich-type polyoxotungstate complexes, [{Mn(bpy)}Na(HO)(MnCl){Mn(HO)}(AsWO)] and [{Mn(bpy)}Na(HO)(MnCl){Mn(HO)}(SbWO)] (bpy = 2,2'-bipyridine), whose structures have been obtained by single-crystal X-ray diffraction (SCXRD), complemented by results obtained from elemental analysis, electrospray ionization mass spectrometry, Fourier transform infrared spectroscopy, and thermogravimetric analysis. They consist of two [B-α-XWO] subunits sandwiching a cyclic assembly of the hexagonal [{Mn(bpy)}Na(HO)(MnCl){Mn(HO)}] and [{Mn(bpy)}Na(HO)(MnCl){Mn(HO)}] moieties, respectively, and represent the first pentanuclear Mn-substituted sandwich-type polyoxometalates (POMs). Both compounds have been synthesized by reacting MnCl·4HO with trilacunary Na[XWO]·27HO (X = As and Sb) POM precursors in the presence of bpy in a 1 M aqueous sodium chloride solution under mild reaction conditions.

Synthesis, Structure, and Magnetic Electrochemical Properties of a Family of Tungstoarsenates Containing Just Co Centers or Both Co and Fe Centers.

The three polyoxotungstates [(NaOH)Co(AsWO)] (1), [(NaOH)(CoOH)Co(AsWO)] (2), and [(CoOH)Co(AsWO)] (3) have been prepared in aqueous solution upon mixing cobalt(II) salts with the ligand [AsWO]. The reaction of 1 or 2 with the Fe ion leads invariably to the same species [(FeOH)(CoOH)Co(AsWO)] (4) possessing three cobalt atoms and a single iron atom. However, if the Fe-containing homologue of compound 1, that is, the polyoxotungstate [(NaOH)Fe(AsWO)] (5), is employed instead to react with the Co ion, the species [(CoOH)Fe(AsWO)] (6) is obtained, having two cobalt atoms and two iron atoms.

Cr-Substituted Heteropoly-16-Tungstates [Cr(B-β-XWO)] (X = Si, Ge): Magnetic, Biological, and Electrochemical Studies.

The dichromium(III)-containing heteropoly-16-tungstates [Cr(B-β-SiWO)] (1) and [Cr(B-β-GeWO)] (2) were prepared via a one-pot reaction of the composing elements in aqueous, basic medium. Polyanions 1 and 2 represent the first examples of Cr-containing heteropolytungstates comprising the octatungstate unit {XWO} (X = Si, Ge). Magnetic studies demonstrated that, in the solid state, the two polyanions exhibit a weak antiferromagnetic interaction between the two Cr centers with J = -3.

Heptanickel(ii) double-cubane core in wells-dawson heteropolytungstate, [Ni7(OH)6(H2O)6(P2W15O56)2](16-).

The hepta-Ni(2+)-containing 30-tungsto-4-phosphate(v) [Ni7(OH)6(H2O)6(P2W15O56)2](16-) (1) has been synthesized in aqueous, slightly basic medium under conventional reaction conditions, and charactarized via different physical methods. Single-crystal XRD showed that 1 consists of a corner-fused double-cubane {Ni7(OH)6(H2O)6}(8+) fragment sandwiched by two trilacunary [P2W15O56](12-) units. Polyanion 1 is solution-stable as shown by (31)P NMR.

Preparation of α1- and α2-isomers of mono-Ru-substituted Dawson-type phosphotungstates with an aqua ligand and comparison of their redox potentials, catalytic activities, and thermal stabilities with Keggin-type derivatives.

Both the α1- and the α2-isomers of mono-ruthenium (Ru)-substituted Dawson-type phosphotungstates with terminal aqua ligands, [α1-P2W17O61Ru(III)(H2O)](7-) (α1-RuH2O) and [α2-P2W17O61Ru(III)(H2O)](7-) (α2-RuH2O), were prepared in pure form by cleavage of the Ru-S bond of the corresponding DMSO derivatives, [α1-P2W17O61Ru(DMSO)](8-) (α1-RuDMSO) and [α2-P2W17O61Ru(DMSO)](8-) (α2-RuDMSO), respectively. Redox studies indicated that α1-RuH2O and α2-RuH2O show proton-coupled electron transfer (PCET), and the Ru(III)(H2O) species was reversibly reduced to Ru(II)(H2O) species and oxidized to Ru(IV)([double bond, length as m-dash]O) species and further to Ru(V)([double bond, length as m-dash]O) species in aqueous solution depending on the pH. Their redox potentials and thermal stabilities were compared with those of the corresponding α-Keggin-type derivatives ([α-XW11O39Ru(H2O)](n-); X = Si(4+) (n = 5), Ge(4+) (n = 5), or P(5+) (n = 4)).

Tetradecanuclear Iron(III)-Oxo Nanoclusters Stabilized by Trilacunary Heteropolyanions.

The tetrameric, multi-Fe(III)-containing polyoxotungstates [Fe14O6(OH)13(P2W15O56)4](31-) (1) and [Na2Fe14(OH)12(PO4)4(A-α-XW9O34)4](20-) (X = Si(IV) (2), Ge(IV) (3)) have been successfully synthesized under conventional reaction conditions in aqueous, slightly acidic (1), or basic (2 and 3) media. Polyanions 1-3 were characterized in the solid state by single-crystal X-ray diffraction, IR spectroscopy, thermogravimetric analysis, and magnetic studies, and in solution by electrochemistry.

Effect of electron (de)localization and pairing in the electrochemistry of polyoxometalates: study of Wells-Dawson molybdotungstophosphate derivatives.

Polyoxometalates (POMs) are inorganic entities featuring extensive and sometimes unusual redox properties. In this work, several experimental techniques as well as density functional theory (DFT) calculations have been applied to identify and assess the relevance of factors influencing the redox potentials of POMs. First, the position of the Mo substituent atom in the Wells-Dawson structure, α1- or α2-P2W17Mo, determines the potential of the first 1e(-) reduction wave.

99Tc and Re incorporated into metal oxide polyoxometalates: oxidation state stability elucidated by electrochemistry and theory.

The radioactive element technetium-99 ((99)Tc, half-life = 2.1 × 10(5) years, β(-) of 253 keV), is a major byproduct of (235)U fission in the nuclear fuel cycle. (99)Tc is also found in radioactive waste tanks and in the environment at National Lab sites and fuel reprocessing centers.

Polyoxometalates functionalized by bisphosphonate ligands: synthesis, structural, magnetic, and spectroscopic characterizations and activity on tumor cell lines.

We report the synthesis and characterization of eight new Mo, W, or V-containing polyoxometalate (POM) bisphosphonate complexes with metal nuclearities ranging from 1 to 6. The compounds were synthesized in water by treating Mo(VI), W(VI), V(IV), or V(V) precursors with biologically active bisphosphonates H(2)O(3)PC(R)(OH)PO(3)H(2) (R = C(3)H(6)NH(2), Ale; R = CH(2)S(CH(3))(2), Sul and R = C(4)H(5)N(2), Zol, where Ale = alendronate, Sul = (2-Hydroxy-2,2-bis-phosphono-ethyl)-dimethyl-sulfonium and Zol = zoledronate). Mo(6)(Sul)(2) and Mo(6)(Zol)(2) contain two trinuclear Mo(VI) cores which can rotate around a central oxo group while Mo(Ale)(2) and W(Ale)(2) are mononuclear species.

Electrochemical behavior of α1/α2-[Fe(H2O)P2W17O61](7-) isomers in solution: experimental and DFT studies.

The unusual redox behavior displayed by the two isomers of the Wells-Dawson phosphotungstate anion [Fe(H(2)O)P(2)W(17)O(61)](7-) is presented. The electrochemical measurements have been performed in aqueous media at different pH values from 0.5 up to 8.

{AsW9O33}-{Mo3S4} based polyoxometalates including a metal-metal bond with Pd or Ni. Synthesis, structure and studies in solution.

Heterometallic cuboidal clusters [Mo(3)S(4)M(H(2)O)(9)Cl](3+) M = Pd or Ni react with the trivacant [AsW(9)O(33)](9-) anion to give tetramodular complexes [(H(2)AsW(9)O(33))(4){Mo(3)S(4)M(H(2)O)(5)}(2)](20-) (M = Pd for anion 2 and M = Ni for anion 3) in good yield. Both anions crystallized as single crystals of potassium salts to give K-2 and K-3 salts which have been characterized structurally by X-ray diffraction. Both compounds are isomorphous and the anions 2 and 3 are described as two dimeric moeties, associated by internal hydrogen bonds, electrostatic interactions involving four outer potassium ion and coordination bonds within a central {M(2)S(2)} unit containing a M-M metallic bond.

Tuning the photochromic properties of molybdenum bisphosphonate polyoxometalates.

Seven hybrid organic-inorganic bisphosphonate molybdenum(VI) polyoxometalate complexes with the general formula [(Mo(3)O(8))(4)(O(3)PC(C(m)H(2m)NRR'R″)(O)PO(3))(4)](8-) (m = 3; R, R', and R″ = H or CH(3)) and [(Mo(3)O(8))(2)(O)(O(3)PC(C(m)H(2m)NRR'R″)(O)PO(3))(2)](6-) (m = 3 or 4; R, R', and R″ = H or CH(3)) have been synthesized and their structures solved using single-crystal X-ray diffraction. These compounds are made of a {Mo(12)} or a {Mo(6)} inorganic core functionalized by various alkylammonium bisphosphonates, with these ligands differing by the length of their alkyl chains and the number of methyl groups grafted on the N atom. The nature of the counter-cations (Na(+), K(+), Rb(+), Cs(+), and/or NH(4)(+)) constituting these materials has also been modulated.

Photoreduction of 99Tc pertechnetate by nanometer-sized metal oxides: new strategies for formation and sequestration of low-valent technetium.

Technetium-99 ((99)Tc) (β(-)(max): 293.7 keV; t(1/2): 2.1 × 10(5) years) is a byproduct of uranium-235 fission and comprises a large component of radioactive waste.

Manganese(III)-containing Wells-Dawson sandwich-type polyoxometalates: comparison with their manganese(II) counterparts.

We present the synthesis and structural characterization, assessed by various techniques (FTIR, TGA, UV-vis, elemental analysis, single-crystal X-ray diffraction for three compounds, magnetic susceptibility, and electrochemistry) of five manganese-containing Wells-Dawson sandwich-type (WDST) complexes. The dimanganese(II)-containing complex, [Na(2)(H(2)O)(2)Mn(II)(2)(As(2)W(15)O(56))(2)](18-) (1), was obtained by reaction of MnCl(2) with 1 equiv of [As(2)W(15)O(56)](12-) in acetate medium (pH 4.7).

Synthesis, structure elucidation, and redox properties of 99Tc complexes of lacunary Wells-Dawson polyoxometalates: insights into molecular 99Tc-metal oxide interactions.

The isotope (99)Tc (β(max), 293.7; half-life, 2.1 × 10(5) years) is an abundant product of uranium-235 fission in nuclear reactors and is present throughout the radioactive waste stored in underground tanks at the Hanford and Savannah River sites.

Structural, magnetic, EPR, and electrochemical characterizations of a spin-frustrated trinuclear Cr(III) polyoxometalate and study of its reactivity with lanthanum cations.

The asymmetric Cr(III) polyoxometalate complex Cs(10)[(gamma-SiW(10)O(36))(2)(Cr(OH)(H(2)O))(3)] x 17 H(2)O (1) has been synthesized in water under atmospheric pressure from the trinuclear precursor [Cr(3)(CH(3)COO)(7)(OH)(2)] and the divacant ligand [gamma-SiW(10)O(36)](8-). Complex 1 is built up of two [gamma-SiW(10)O(36)](8-) Keggin units sandwiching a trinuclear {(Cr(III)(OH)(H(2)O))(3)} fragment where the paramagnetic centers are bridged by three mu-OH ligands forming a nearly isosceles triangle. The magnetic properties of this spin-frustrated system have thus been interpreted considering a 2-J Hamiltonian showing that the Cr(III) ions are antiferromagnetically coupled and that 1 possesses an S = 3/2 ground state with an S = 1/2 first excited state located at 11 cm(-1).

Iron polyoxometalate single-molecule magnets.

Iron sandwich on a tungstate bun: Two new polyoxotungstates with paramagnetic iron(III) heteroatoms (see structure, W blue, Fe yellow, O red) possess S=15/2 and S=5 ground states. Both compounds are single-molecule magnets, and the hexairon species shows large hysteresis (see picture) and quantum tunneling effects at low temperature. Electrochemical studies indicate that these species are stable in solution for a wide range of pH values.

Self-assembly of polyoxometalate macroanion-capped pd0 nanoparticles in aqueous solution.

The self-assembly behavior of polyoxometalate (POM) macroanion-capped 3-nm-radius Pd (0) nanoparticles in aqueous solution is reported. Pd(0) nanoparticles are synthesized from reducing K(2)PdCl(4) by using Dawson-type V-substituted POM K(9)[H(4)PV (IV)W(17)O(62)] (HPV(IV)) clusters as the reductant and stabilizer simultaneously in acidic aqueous solutions. The starting molar ratio of K(2)PdCl(4) to HPV(IV) (R value) in solution is important to the formation of Pd nanoparticles.

Semi-vacant Wells-Dawson anions. Synthesis of tri-tungsten-vacant derivatives and crystallographic studies of [alphabetabetaalpha-(Cu(II)OH2)2(Cu(II))2(AsW15(OH2)3(OH)O52)2]12-.

The tri-tungsten-vacant polyoxometalate, [alpha-AsW15(OH)4O52]13-, derived from the semi-vacant Wells-Dawson complex [alpha-AsW18(OH)4O58]7-, reacts with the late-transition metal cations, Cu(II) or Zn(II), to form sandwich-type species; the X-ray crystal structure of [alphabetabetaalpha]-(Cu(II)OH2)2(Cu(II))2(AsW15(OH2)3(OH)O52)2]12-, prepared by the acidification of [alphabetabetaalpha]-(Cu(II)OH2)2(Cu(II))2(AsW15(OH)4O52)2]18-, reveals that the missing heteroatoms are distal to the central Cu4 unit and the vertices of the vacant tetrahedron are occupied by one OH- and three OH2 groups.

Multi-iron wells-Dawson heteropolytungstates. Electrochemical probing of siderophoric behavior in sandwich-type complexes.

The demetalation process of 10 multi-iron Wells-Dawson polyoxometalates is studied by cyclic voltammetry and controlled potential coulometry. Eight sandwich-type complexes (alphaalphaalphaalpha-Na(16)[(NaOH(2))(2)(Fe(III))(2)(X(2)W(15)O(56))(2)], alphaalphabetaalpha-Na(14)[(NaOH(2))(Fe(III)OH(2))(Fe(III))(2)(X(2)W(15)O(56))(2)], alphabetabetaalpha-Na(12)[(Fe(III)OH(2))(2)(Fe(III))(2)(X(2)W(15)O(56))(2)], and alphabetabetaalpha-Na(14)[(Mn(II)OH(2))(2)(Fe(III))(2)(X(2)W(15)O(56))(2)] (where X = P(V) or As(V))) and two monomeric complexes (alpha-Na(11)[(P(2)(Fe(III)Cl)(2)(Fe(III)OH(2))W(15)O(59))] and alpha-Na(11)[(As(2)(Fe(III)Cl)(2)Fe(III)OH(2))W(15)O(59))]) were selected for this study. All 10 complexes show Fe(III) waves which are well-separated from the redox activity of the W(VI) centers.

Structure, magnetism, and electrochemistry of the multinickel polyoxoanions [Ni6As3W24O94(H2O)2]17-, [Ni3Na(H2O)2(AsW9O34)2]11-, and [Ni4Mn2P3W24O94(H2O)2]17-.

The three novel, multi-nickel-substituted heteropolytungstates [Ni(6)As(3)W(24)O(94)(H(2)O)(2)](17)(-) (1), [Ni(3)Na(H(2)O)(2)(AsW(9)O(34))(2)](11)(-) (2), and [Ni(4)Mn(2)P(3)W(24)O(94)(H(2)O)(2)](17)(-) (3) have been synthesized and characterized by IR, elemental analysis, electrochemistry, and magnetic studies. Single-crystal X-ray analysis was carried out on Na(16.5)Ni(0.