Rational addition of capping groups to the phosphomolybdate Keggin anion [PMo12O40](3-) by mild, non-aqueous reductive aggregation

Controlled reductive assembly of capped Keggin anions [PMo(12)O(40)(ML(m))(n)](3-) has been achieved by reduction of [PMo(12)O(40)](3-) with sodium-mercury amalgam in the presence of metal halides, as exemplified by the rational syntheses of mono-capped [PMo(12)O(40){Co(MeCN)(2)}](3-) and bi-capped [PMo(12)O(40)(VO)(2)](3-) and [PMo(12)O(40)Sb(2)](3-).     

Spectroscopic properties of neodymium(III)-containing polyoxometalates in aqueous solution

The spectroscopic properties of the neodymium(III)-containing polyoxometalates (POMs) [Nd(PW(11)O(39))(2)](11-), [Nd(PMo(2)W(9)O(39))(2)](11-), [Nd(PMo(4)W(7)O(39))(2)](11-), [Nd(PMo(6)W(5)O(39))(2)](11-), [Nd(SiMo(2)W(9)O(39))(2)](13-), [Nd(P(2)W(17)O(61))(2)](17-), [NdW(10)O(36)](9-), [NdP(5)W(30)O(110)](12-) and [NdAs(4)W(40)O(140)](25-) are described. Absorption spectra of aqueous solutions of the complexes have been recorded and the transition intensities are parameterised in terms of the Judd-Ofelt intensity parameters Omega(lambda) (lambda=2, 4, 6). Marked differences were found between the luminescence lifetimes of the complexes of the type Nd(POM) and those of the type Nd(POM)(2), due to a better shielding of the neodymium(III) ions from the bulk water molecules in the latter type of complexes.     

Hydrogen-bonded assemblies of two-electron reduced mixed-valence [XMo12O40] (X = P and Si) with p-phenylenediamines

Hydrogen-bonded assemblies of the two-electron reduced mixed-valence Keggin clusters [PMo(12)O(40)](5-) and [SiMo(12)O(40)](6-) were obtained by the one-pot electron-transfer reactions between p-phenylenediamine (PPD) or 2,3,5,6-tetramethyl-PPD (TMPPD) (donors) and H(+)(3)[PMo(12)O(40)](3-) or H(+)(4)[SiMo(12)O(40)](4-) (acceptors) in CH(3)CN. The redox states of the [PMo(12)O(40)](5-) and [SiMo(12)O(40)](6-) clusters were confirmed by the redox titrations and electronic absorption measurements. In (HPPD(+))(3)(H(+))(2)[PMo(12)O(40)](5-)(CH(3)CN)(3-6) (1), the N-H ~ O hydrogen-bonded interactions between the monoprotonated HPPD(+) (or diprotonated H2PPD(2+)) and the [PMo(12)O(40)](5-) resulted in a windmill-like assembly and hydrophilic one-dimensional channels are formed with a cross-sectional area of 0.065 nm(2), and these are filled by the CH(3)CN molecules. Also, the CH(3)CN molecules in salt 1 were removed by immersing the single crystals of 1 into H(2)O, CH(3)OH, and C(2)H(5)OH solvents. In the compound, (HTMPPD(+))(6)[SiMo(12)O(40)](6-)(CH(3)CN)(6) (2), the N-H ~ O hydrogen-bonded interactions between the monoprotonated HTMPPD(+) molecules and the [SiMo(12)O(40)](6-) formed a "Saturn-ring"-like assembly. Each Saturn-ring was arranged into an hexagonally packed array via hydrogen-bonded and π-stacking interactions of HTMPPD(+), while the CH(3)CN solvent present in salt 2 are only found in the zero-dimensional isolated cavities.     

Formation of p-phenylenediamine-crown ether-[PMo12O40]4- salts

Electron transfer from the electron donor of p-phenylenediamine (PPD) to the electron acceptor of (H+)3[PMo12O40]3- forms a one-electron-reduced Keggin cluster of [PMo12O40]4-, bearing a S = 1/2 spin, while proton transfer from the proton donor of (H+)3[PMo12O40]3- to the proton acceptor of PPD yielded mono- and diprotonated cations of 4-aminoanilinium (HPPD+) and p-phenylenediammonium (H2PPD2+). By introduction of crown ether receptors during the crystallization process, supramolecular cations of (HPPD+)(crown ethers) and/or (H2PPD2+)(crown ethers) were successfully introduced into three new alpha-[PMo12O40]4- salts of (H2PPD2+)2([12]crown-4)4[PMo12O40]4- (1), (HPPD+)4([15]crown-5)4[PMo12O40]4- (2), and (HPPD+)2(H2PPD2+)([18]crown-6)4[PMo12O40]4- (3) as the countercation. The protonated states of PPD and molecular-assembly structures of the supramolecular cations depended on the size of the crown ethers. In salt 3, a novel mixed-protonated state of HPPD+ and H2PPD2+ was confirmed to be complexed in the cation structure. According to the changes in the cation structures, the anion arrangements were modulated from those of the two-dimensional layer for salt 1 to the isolated cluster for salts 2 and 3. The temperature-dependent magnetic susceptibilities of salts 1-3 were consistent with the isolated spin arrangements of [PMo12O40]4-. The electronic spectra of salts 1-3 indicated the intervalence optical transition from pentavalent Mo(V) to hexavalent Mo(VI) ions within the [PMo12O40]4- cluster. Temperature-dependent electron spin resonance spectra of salt 2 revealed the delocalization-localization transition of the S = 1/2 spin at 60 K. The spin on the [PMo12O40]4- cluster was localized on a specific Mo(V) site below 60 K, which was thermally activated with an activation energy of 0.015 eV.     

Trivalent lanthanide lacunary phosphomolybdate complexes: a structural and spectroscopic study across the series [Ln(PMo11O39)2]11-

We report the syntheses and crystal structures of (NH4)11[Ln(III)(PMo11O39)2.xH2O (where Ln = every trivalent lanthanide cation except promethium) in which two lacunary [PMo11O39]7- anions sandwich an 8-coordinate Ln(III) cation to yield the complex anion, [LnIII(PMo11O39)2]11-. The 14 salts crystallise in two different space groups, C2/c or P1, but the LnIII containing anions are isostructural across the whole series, a very rare example of such a complete study. Solid state and solution 31P NMR, Raman and IR spectroscopies have been used to prove the stability of [Ln(PMo11O39)2]11- in aqueous solution. As expected, the LnIII cation contracts across the series and the Ln-O bond distances decrease uniformly. Interestingly, the splitting in the nu(P-O) mode within the [PMo11O39]7- unit increases uniformly across the series, which we attribute to the stronger interaction with the smaller, higher charge density LnIII cation as the series is traversed. For the 31P NMR measurements a direct comparison of Lanthanide Induced (paramagnetic) Shift could be made with the analogous [P(W11O39)2]11- complexes.     

The ball-shaped heteropolytungstates [[Sn(CH3)2(H2O)]24[Sn(CH3)2]12(A-XW9O34)12]36- (X=P, As): stability, redox and electrocatalytic properties in aqueous media

The electrochemical behavior of the ball-shaped heteropolytungstates [[Sn(CH(3))(2)(H(2)O)](24)[Sn(CH(3))(2)](12)(A-XW(9)O(34))(12)](36-) (X=P, 1; As, 2) was examined in aqueous electrolytes by redissolution of their respective mixed cesium-sodium salts Cs(14)Na(22)[[Sn(CH(3))(2)(H(2)O)](24)[Sn(CH(3))(2)](12) (A-PW(9)O(34))(12)]149 H(2)O (Cs(14)-1) and Cs(14)Na(22)[[Sn(CH(3))(2)(H(2)O)](24)[Sn(CH(3))(2)](12)(A-AsW(9)O(34))(12)]149 H(2)O (Cs(14)-2). In the studied media, Cs(14)-2 is readily soluble in contrast to the significantly less soluble Cs(14)-1. The solubility of Cs(14)-1 is increased by the presence of Li(+) ions in solution. Gel filtration studies with 1 and 2 rule out a decay of the dodecameric spherical assemblies to Keggin-based monomers on the timescale of the experiment. By UV/Vis spectroscopy and cyclic voltammetry, 2 was found to be significantly less stable than 1 and both polyanions also show rather different decomposition pathways. Polyanion 1 collapses first into Keggin-type monomers which might contain the trilacunary [A-alpha-PW(9)O(34)](9-). The final monomeric species obtained from 1 appears to be very similar to [PW(11)O(39)](7-), which is the final transformation product of [A-alpha-PW(9)O(34)](9-) in the same media. In contrast, 2 does not seem to follow an analogous transformation pathway as that of the trilacunary [A-alpha-AsW(9)O(34)](9-). Importantly, stabilization of 1 is observed in chloride media. The fairly long-term stability of 1 in 1 M LiCl, pH 3, has allowed for its electrochemical study to be carried out. The solid-state cyclic voltammogram of 1 entrapped in a carbon paste electrode shows the same characteristics as 1 dissolved in chloride solutions, thus supporting the conclusion that the polyanion is stable in these environments. Controlled potential coulometry on 1 indicates that the number of electrons consumed in the first wave is larger than twenty. To our knowledge, 1 constitutes the first example of a molecule that can take up such a large number of electrons resulting in a chemically reversible W-wave. These properties show promise for future fundamental and applied studies. Polyanion 1 is also efficient in the electrocatalytic reduction of NO(x), including nitrate. Finally, a remarkable interaction was found between 1 and NO, a highly promising feature for biomimetic applications.     

Zeolite ionic crystals assembled through direct incorporation of polyoxometalate clusters within 3D metal-organic frameworks

Polyoxometalate-based metal-organic frameworks {[Gd(dpdo)(4)(H(2)O)(3)](PMo(12)O(40))(H(2)O)(2)CH(3)CN}(n) (2), {[Dy(dpdo)(4)(H(2)O)(3)](PMo(12)O(40))(H(2)O)(20CH(3)CN}(n) (3), {[Gd(dpdo)(4)(H(2)O)(3)](H(3)O)(SiMo(12)O(40))(dpdo)(0.5)(CH(3)CN)(0.5) (H(2)O)(3)}(n) (4), {[Ho(dpdo)(4)(H(2)O)(3)](H(3)O)(SiMo(12)O(40))(dpdo)(0.5)(CH(3)CN)(0.5)(H(2)O)(3)}(n) (5), {[Ni(dpdo)(2)(CH(3)CN) (H(2)O)(2)](2)(SiMo(12)O(40))(H(2)O)(2)}(n) (6), and {[Ni(dpdo)(3)](4)(PW(12)O(40))(3)[H(H(2)O)(27)(CH(3)CN)(12)]}(n) (7) (where dpdo is 4,4'-bipyridine-N,N'-dioxide) were constructed via self-assembly by embedding Keggin-type polyanions within the intercrystalline voids as guests or pillars. Compounds 2 and 3 are isomorphic and exhibit three-dimensional (3D) noninterwoven 64 frameworks with distorted-honeycomb cavities occupied by the polyanions. Compounds 4 and 5 are comprised of 3D noninterwoven frameworks formed by linking the adjacent folded sheets through hydrogen bonds and pi-pi stacking interactions relative to the free isolated dpdo ligand. Compound 6 is a pillar-layered framework with the [SiMo(12)O(40)](4-) anions located on the square voids of the two-dimensional bilayer sheets formed by the dpdo ligands and nickel(II) ions. Compound 7 is a 3D metal-organic framework formed by nickel(II) and 4,4'-bipyridine-N,N'-dioxide with the globular Keggin-structure [PW(12)O(4)](3-) anion as the template. A large protonated water cluster H(+)(H(2)O)(27) is trapped and stabilized within the well-modulated cavity.     

Methoxide of an Anderson-type polyoxometalate and its conversion to a new type of species, [IMo9O32(OH)(OH2)3]4-

A totally new type of polyoxometalate, [IMo(9)O(32)(OH)(OH(2))(3)](4)(-), has been synthesized by reacting [IMo(6)O(22)(OMe)(2)](3)(-) with water. The [IMo(9)O(32)(OH)(OH(2))(3)](4)(-) anion further transforms into [(IMo(7)O(26))(2)](6)(-), a molecular oxide that has a rutile core, in dry acetonitrile, while it stays intact for several hours in wet acetonitrile.     

Cation-directed synthesis of tungstosilicates. 1. Syntheses and structures of K10A-alpha-[SiW9O34].24H2O,of the sandwich-type complex K10.75[Co(H2O)6]0.5[Co(H2O)4Cl]0.25A-alpha-[K2(Co(H2O)2)3(SiW9O34)2].32H2O and of Cs15[K(SiW11O39)2].39H2O

The influence of the nature of alkali metal cations on the structure of the species obtained from the trivacant precursor A-alpha-[SiW(9)O(34)](10-) has been studied. Starting from the potassium salt 1, K(10)A-alpha-[SiW(9)O(34)].24H(2)O, the sandwich-type complex 2, K(10.75)[Co(H(2)O)(6)](0.5)[Co(H(2)O)(4)Cl](0.25)A-alpha-[K(2)(Co(H(2)O)(2))(3)(SiW(9)O(34) )(2)].32H(2)O, has been obtained. The crystal structures of these two compounds consist of two A-alpha-[SiW(9)O(34)](10-) anions linked by a set of potassium (1) or cobalt plus potassium cations (2), and the relative orientation of the two half-anions is the same. Attempts to link two A-alpha-[SiW(9)O(34)](10-) anions by tungsten atoms instead of cobalt failed whatever the alkali metal cation. Moreover, the nondisordered structure of Cs(15)[K(SiW(11)O(39))(2)].39H(2)O is described. Two [SiW(11)O(39)](8-) anions are linked through a potassium cation with a "trans-oid" conformation, and the potassium occupies a cubic coordination site.     

A monovacant heteropolytungstate thioderivative: Synthesis and characterization of [(PW11O39)2(H4Mo4S4O6)](10-) and related isomers

[(PW(11)O(39))(2)(Mo(4)S(4)O(4)(OH(2))(2))](10-) anions were obtained through the stereospecific addition of the [Mo(2)S(2)O(2)](2+) oxothiocation to the monovacant alpha-[PW(11)O(39)](7-) anion. K(10)[(PW(11)O(39))(2)(Mo(4)S(4)O(4)(OH(2))(2))].25H(2)O has been isolated as crystals and characterized by X-ray diffraction. The structure revealed a "sandwich-like" dimer of two alpha-[PW(11)O(39)](7-) subunits assembled by the noteworthy central cluster [H(4)Mo(4)S(4)O(6)]. The crystallization of the crude product produces an isomerically pure compound, which was characterized by (31)P and (183)W NMR. IR data were also supplied. In solution, the compound isomerizes, giving a second diastereoisomer. A kinetic experiment, carried out by (31)P NMR, allowed the conditions of the thermodynamic equilibrium to be determined. A structural relationship between the two isomers is proposed, fully consistent with NMR data. Cisoid and transoid isomers result in the relative disposition of each [PW(11)O(39)](7-) subunit, either staggered or eclipsed. An investigation of the formation of the [Mo(2)O(2)S(2)](2+) unit from the polycondensed cyclic precursor [Mo(10)S(10)O(10)(OH)(10)(H(2)O)(5)] and the aggregation process resulting in the oxothio [(PW(11)O(39))(2)(Mo(4)S(4)O(4)(OH(2))(2))](10-) compound has been undertaken. The studies were monitored by (31)P NMR and UV-vis spectroscopies. The reaction is quantitative in nearly stoichiometric conditions.     

Tetravalent metal complexation by Keggin and lacunary phosphomolybdate anions

We report the synthesis, spectroscopic and structural characterization, and computational analysis of a series of phosphomolybdate complexes with tetravalent metal cations. The reaction between Ce (IV) and Th (IV) with phosphomolybdate at the optimum pH for the stabilization of the lacunary heteropolyoxometalate anion, [PMo 11O 39] (7-), results in the formation of compounds containing the anions [Ce(PMo 11O 39) 2] (10-) and [Th(PMo 11O 39) 2] (10-), respectively. Single crystal X-ray diffraction analysis was performed on salts of both species, Cs 10[Ce(PMo 11O 39) 2].20H 2O and (NH 4) 10[Th(PMo 11O 39) 2].22H 2O. In both anionic complexes the f-block metal cation is coordinated to the four unsaturated terminal lacunary site oxygens of each [PMo 11O 39] (7-) anion, yielding 8 coordinate sandwich complexes, analogous to previously prepared related complexes. Spectroscopic characterization points to the stability of these complexes in solution over a reasonably wide pH range. Density functional analysis suggests that the Ce-O bond strength in [Ce(PMo 11O 39) 2] (10-) is greater than the Th-O bond strength in [Th(PMo 11O 39) 2] (10-), with the dominant bonding interaction being ionic in both cases. In contrast, under similar reaction conditions, the dominant solid state Zr (IV) and Hf (IV) complexes formed contain the anions [Zr(PMo 12O 40)(PMo 11O 39)] (6-) and [Hf(PMo 12O 40)(PMo 11O 39)] (6-), respectively. In these complexes the central Group 4 d-block metal cations are coordinated to the four unsaturated terminal lacunary site oxygens of the [PMo 11O 39] (7-) ligand and to four bridging oxygens of a plenary Keggin anion, [PMo 12O 40] (3-). In addition, (NH 4) 5{Hf[PMo 12O 40][(NH 4)PMo 11O 39]}.23.5H 2O can be crystallized as a minor product. The structure of the anion, {Hf[PMo 12O 40][(NH 4)PMo 11O 39]} (5-), reveals coordination of the central Hf (IV) cation via four bridging oxygens on both the coordinated [PMo 11O 39] (7-) and [PMo 12O 40] (3-) anions. Unusually, the highly charged lacunary site remains uncoordinated to the Hf metal center but instead interacts with an ammonium cation. (31)P NMR indicates that complexation of the Keggin anion, [PMo 12O 40] (3-), to Hf (IV) and Zr (IV) will stabilize the Keggin anion to a much higher pH than usually observed.     

VO(H2O)5]H[PMo12O40]-catalyzed nitration of alkanes with nitric acid

[VO(H2O)5]H[PMo12O40], which contains vanadyl counter cations and PMo12O40(3-), can act as a catalyst for the nitration of various alkanes including alkylbenzenes using nitric acid as a nitrating agent in acetic acid at 356 K.     

Two sandwich arsenomolybdates based on the new building block As(iii)Mo(7)O(27)(9-): [Cr(2)(AsMo(7)O(27))(2)](12-) and [Cu(2)(AsMo(7)O(27))(2)](14-)

The polyanions [Cr(2)(AsMo(7)O(27))(2)](12-) () or [Cu(2)(AsMo(7)O(27))(2)](14-) () have sandwich-like structures wrapping two transition metals between two [As(iii)Mo(7)O(27)](9-) fragments, and the fragment is unprecedented and can be viewed as a mono-capped hexavacant B-alpha-Keggin subunit with a central AsO(3) group.     

Voltammetric Reduction of alpha- and gamma-[S2W18O62]4- and alpha-, beta-, and gamma-[SiW12O40]4-: isomeric dependence of reversible potentials of polyoxometalate anions using data obtained by novel dissolution and conventional solution-phase processes

Comparative studies on the voltammetric reduction of the alpha and gamma isomers of Dawson [S(2)W(18)O(62)](4)(-) and alpha, beta, and gamma forms of Keggin [SiW(12)O(40)](4)(-) polyoxometalate anions have been undertaken. For the six reversible one-electron [S(2)W(18)O(62)](4)(-)(/5)(-)(/6)(-)(/7)(-)(/8)(-)(/9)(-)(/10)(-) processes in acetonitrile, reversible potentials (E(0)(')) were found to be independent of isomeric form within experimental error (+/-5 mV). However, because both the alpha and gamma* isomers of [Bu(4)N](4)[S(2)W(18)O(62)] are insoluble in water, solid-state voltammetric studies with microcrystals adhered to electrode surfaces in contact with aqueous Et(4)NCl and Bu(4)NCl electrolyte media were also possible. Although no isomeric distinction was again detected in the solid-state studies, it was found that reduction of adhered solid by four or more electron equivalents led to rapid dissolution. When Et(4)NCl was the electrolyte, this dissolution process coupled with potential cycling experiments enabled conventional solution-phase data to be obtained in water for the analogous six one-electron reduction steps previously detected in acetonitrile. A strong medium effect attributed to Lewis acidity effects was apparent upon comparison with E(0)(') data obtained in water and acetonitrile. In contrast, with the [SiW(12)O(40)](4)(-) system, E(0)(') values for the [SiW(12)O(40)](4)(-)(/5)(-)(/6)(-)(/7)(-) processes in acetonitrile exhibited a larger (about 70 mV) dependence on isomeric form, and the isomerization step, [gamma-SiW(12)O(40)](6)(-)--> [alpha-SiW(12)O(40)](6)(-), was detected on the voltammetric time scale. The influence of isomeric form on reversible potential data is considered in terms of structural and charge density differences exhibited in the [S(2)W(18)O(62)](4)(-) and [SiW(12)O(40)](4)(-) systems studied in this paper and published data available on the alpha, beta, gamma, and gamma isomers of [As(2)W(18)O(62)](6)(-) and [P(2)W(18)O(62)](6)(-) Dawson anions and Keggin systems.     

The elusive tetrasulfate anion [S4O13](2-)

Sulfates united: the unique tetrasulfate S(4)O(13)(2-) anion was observed in the structure of (NO(2))(2)[S(4)O(13)] that forms in the reaction of N(2)O(5) with SO(3). Theoretical investigations show that the anion is a stable member of the polysulfate series [S(n)O(3n+1)](2-), which was investigated up to n=11.     

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(0.25)[Ni(6)As(3)W(24)O(94)(H(2)O)(2)].54H(2)O, which crystallizes in the triclinic system, space group P1, with a = 17.450(4) A, b = 17.476(4) A, c = 22.232(4) A, alpha = 85.73(3) degrees, beta = 89.74(3) degrees, gamma = 84.33(3) degrees, and Z = 2, Na(11)[Ni(3)Na(H(2)O)(2)(AsW(9)O(34))(2)].30.5H(2)O, which crystallizes in the triclinic system, space group P1, with a = 12.228(2) A, b = 16.743(3) A, c = 23.342(5) A, alpha = 78.50(3) degrees, beta = 80.69(3) degrees, gamma = 78.66(3) degrees, and Z = 2, and Na(17)[Ni(4)Mn(2)P(3)W(24)O(94)(H(2)O)(2)].50.5H(2)O, which crystallizes in the monoclinic system, space group P2(1)/c, with a = 17.540(4) A, b = 22.303(5) A, c = 35.067(7) A, beta = 95.87(3) A, and Z = 4. Polyanion 1 consists of two B-alpha-(Ni(3)AsW(9)O(40)) Keggin moieties linked via a unique AsW(6)O(16) fragment, leading to a banana-shaped structure with C(2)(v)() symmetry. The mixed-metal tungstophosphate 3 is isostructural with 1. Polyanion 2 consists of two lacunary B-alpha-[AsW(9)O(34)](9)(-) Keggin moieties linked via three nickel(II) centers and a sodium ion. Electrochemical studies show that 1-3 exhibit a unique and reproducible voltammetric pattern and that all three compounds are stable in a large pH range. An investigation of the magnetic properties of 1-3 indicates that the exchange interactions within the trimetal clusters are ferromagnetic. However, for 1 and 3 intra- and intermolecular interactions between different trinuclear clusters are also present.     

Solid-State and solution studies of [Ln(n)(SiW11O39)] polyoxoanions: an example of building block condensation dependent on the nature of the rare earth

The reactivity of the [alpha-SiW(11)O(39)](8-) monovacant polyoxometalate with lanthanide has been investigated for four different trivalent rare-earth cations (Ln = Nd(III), Eu(III), Gd(III), Yb(III)). The crystal structures of KCs(4)[Yb(alpha-SiW(11)O(39))(H(2)O)(2)] x 24H(2)O (1), K(0.5)Nd(0.5)[Nd(2)(alpha-SiW(11)O(39))(H(2)O)(11)] x 17H(2)O (2a), and Na(0.5)Cs(4.5)[Eu(alpha-SiW(11)O(39))(H(2)O)(2)] x 23H(2)O (3a) are reported. The solid-state structure of compound 1 consists of linear wires built up of [alpha-SiW(11)O(39)](8-) anions connected by Yb(3+) cations, while the linkage of the building blocks by Eu(3+) centers in 3a leads to the formation of zigzag chains. In 2a, dimeric [Nd(2)(alpha-SiW(11)O(39))(2)(H(2)O)(8)](10-) entities are linked by four Nd(3+) cations. The resulting chains are connected by lanthanide ions, leading to a bidimensional arrangement. Thus, the dimensionality, the organization of the polyoxometalate building units, and the Ln/[alpha-SiW(11)O(39)](8-) ratio in the solid state can be tuned by choosing the appropriate lanthanide. The luminescent properties of compound 3a have been studied, showing that, in solution, the polymer decomposes to give the monomeric complex [Eu(alpha-SiW(11)O(39))(H(2)O)(4)](5-). The lability of the four exogenous ligands connected to the rare earth must allow the functionalization of this lanthanide polyanion.     

Synthesis and structure of QD-6: a novel aluminoborate constructed from unprecedented [B@Al6O24] and polyborate clusters

A novel aluminoborate (NH(4))(6)[C(5)NH(12)](6)[Al(12)B(65)O(105)(OH)(33)]·(H(2)O)(15) (QD-6), has been synthesized under mild hydrothermal conditions and characterized by IR, elemental analysis, TGA, powder and single-crystal X-ray diffractions. This compound crystallizes in the rhombohedral space group R3 (No. 148) with the lattice constants a = 23.7421(2) ?, c = 24.7699(3) ?, V = 12091.9(2) ?(3), and Z = 3. QD-6 consists of two unprecedented aluminoborate clusters, [Al(6)B(34)O(54)(OH)(18)](6-) and [Al(6)B(31)O(51)(OH)(15)](6-), which are built from the same hexagon-like [B@Al(6)O(24)] clusters and [B(11)O(17)(OH)(6)] or [B(10)O(16)(OH)(5)] polyborates.     

A novel polyoxovanadium borate incorporating an organic amine ligand: synthesis and structure of [V12B16O50(OH)7(en)]7-

A novel 1D chain organic-inorganic hybrid polyoxovanadium borate Na[V(12)B(16)O(50)(OH)(7)(en)](2)(enH(2))(6)(enH)(2)(OH)(H(2)O)(19) (1, en = ethylenediamine), based on a [V(12)B(16)O(50)(OH)(7)(en)](7-) cluster unit, has been hydrothermally synthesized and characterized. Interestingly, organic amine is incorporating into the V(12)B(16) clusters.     

In situ electro-deposition of Pt micro-nano clusters on the surface of {[PMo12O40]3-/PAMAM}n multilayer composite films and their electrocatalytic activities regarding methanol oxidation

The {[PMo(12)O(40)](3-)/PAMAM}(n) multilayer films are prepared by LBL electrostatic assembly technique, and their uniform and homogeneous traits have been verified by cyclic voltammetry. The {[PMo(12)O(40)](3-)/PAMAM}(n) multilayer films with PAMAM as the outmost layer, having an open structure and exhibiting good penetrability for the solvent molecules at low pH, are used as matrices for electro-deposition of Pt micro-nano clusters in situ. X-ray photoelectron spectroscopy (XPS) analysis and field emission scanning electron microscope (FE-SEM) characterization show that the unique Pt micro-nano clusters with flower-like structure have been immobilized on the surface of {[PMo(12)O(40)](3-)/PAMAM}(n) multilayer films. The morphologies of Pt micro-nano clusters are influenced by electro-deposition conditions such as deposition potential, deposition time, and the number of layers of {[PMo(12)O(40)](3-)/PAMAM}(n) multilayer films. Pt(-clusters)-{PMo(12)/PAMAM}(3) composite films demonstrate good electrocatalytic activities regarding methanol oxidation and improved tolerance of CO.