Encapsulation of the vanadium substituted Keggin polyoxometalates [α-PVWO] and [α-PVWO] in HKUST-1.

Two POM@MOF hybrid materials composed of a copper-based metal-organic framework (MOF) [Cu(CHO)(HO)] (HKUST-1) encapsulating vanadium-substituted Keggin polyoxometalates (POM), [α-PVWO] () and [α-PVWO] (), were prepared and characterized. PVW@HKUST-1 and PVW@HKUST-1 were synthesized hydrothermally by self-assembly of HKUST-1 in the presence of the preformed POMs, [α-PVWO] and [α-PVWO], respectively. The two POM@MOF composites were characterized by X-ray diffraction, TGA, BET surface area analysis and FT-IR and Raman spectroscopy.

Organo-Functionalized Lacunary Double Cubane-Type Oxometallates: Synthesis, Structure, and Properties of [(M Cl) (V O) {((HOCH CH )(H)N(CH CH O))(HN(CH CH O) )} ] (M=Co, Zn).

Organofunctionalized tetranuclear clusters [(M Cl) (V O) {((HOCH CH )(H)N(CH CH O))(HN(CH CH O) )} ] (1, M=Co, 2: M=Zn) containing an unprecedented oxometallacyclic {M V Cl N O } (M=Co, Zn) framework have been prepared by solvothermal reactions. The new oxo-alkoxide compounds were fully characterized by spectroscopic methods, magnetic susceptibility measurement, DFT and ab initio computational methods, and complete single-crystal X-ray diffraction structure analysis. The isostructural clusters are formed of edge-sharing octahedral {VO N} and trigonal bipyramidal {MO NCl} units.

Organo-functionalized metal-oxide clusters: synthesis and characterization of the reduced cationic species [NaV(IV)6O6{(OCH2CH2)2NH}6]+.

A new heteropolyoxovanadium compound, [NaV6O6{(OCH2CH2)2NH}6]·(OH)0.5Cl0.5·3(H2O), was synthesized and characterized by single-crystal X-ray diffraction analysis, cyclic voltammetry, FTIR and UV-vis spectroscopy, and TGA.

Functionalized metal oxide clusters: synthesis, characterization, crystal structures, and magnetic properties of a novel series of fully reduced heteropolyoxovanadium cationic clusters decorated with organic ligands--[MVIV6O6[(OCH2CH2)2N(CH2CH2OH)]6]X (M = Li, X = Cl x LiCl; M = Na, X = Cl x H2O; M = Mg, X = 2Br x H2O; M = Mn, Fe, X = 2Cl; M = Co, Ni, X = 2Cl x H2O).

A novel series of fully reduced heteropolyoxovanadium(IV) compounds, [MVIV6O6[(OCH2CH2)2N(CH2CH2OH)]6]X (1, M = Li, X = Cl x LiCl; 2, M = Na, X = Cl x H2O; 3, M = Mg, X = 2Br x H2O; 4, M = Mn, X = 2Cl; 5, M = Fe, X = 2Cl; 6, M = Co, X = 2Cl x H2O; 7, M = Ni, X = 2Cl x H2O), have been synthesized and characterized by FT-IR and UV-vis spectroscopies, thermogravimetric analysis, elemental analysis, manganometric titration, temperature-dependent magnetic susceptibility measurements, bond valence sum calculations, X-ray powder diffraction, and single-crystal X-ray diffraction analyses. The structures of the crystals are comprised of discrete units of fully reduced cluster cations, [MVIV6O6[(OCH2CH2)2N(CH2CH2OH)]6]n+, counterions (chloride or bromide), and water of crystallization (in the case of 2, 3, 6, 7). In each case the cluster ion is composed of a fully reduced cyclic [MV6N6O18] (M = Li, Na, Mg, Mn, Fe, Co, Ni) framework decorated with six triethanolamine ligands.

A novel series of materials composed of arrays of vanadium oxide container molecules, [V18O42(X)] (X = H2O, Cl-, Br-): synthesis and characterization of [M2(H2N(CH2)2NH2)5][(M(H2N(CH2)2NH2)2]2V18O42(X)]. 9H2O (M = Zn, Cd).

The synthesis and characterization of the novel systems [Zn(2)(H(2)N(CH(2))(2)NH(2))(5)][(Zn(H(2)N(CH(2))(2)NH(2))(2))(2)V(18)O(42)(H(2)O)].9H(2)O (1), [Cd(2)(H(2)N(CH(2))(2)NH(2))(5)][(Cd(H(2)N(CH(2))(2)NH(2))(2))(2)V(18)O(42)(Br)].9H(2)O (2), and [Zn(2)(H(2)N(CH(2))(2)NH(2))(5)][(Zn(H(2)N(CH(2))(2)NH(2))(2))(2)V(18)O(42)(Cl)].

A novel cationic heteropolyoxovanadium(IV) cluster functionalized with organic ligands: synthesis and characterization of the fully reduced species [Mn(II)V(IV)6O6[(OCH2CH2)2N(CH2CH2OH)]6]Cl2.

The solvothermal reaction of (HOCH2CH2)3N with [(n-C4H9)4N]3[H3V10O28] and MnCl2 x 4H2O in CH3CN and CH3OH yields a novel cationic heteropolyoxovanadium(IV) cluster, [Mn(II)V(IV)6O6[(OCH2CH2)2N(CH2CH2OH)]6]2+, containing a fully reduced new cyclic [MnV6N6O18] core with the Anderson structure.

Novel water clusters in the crystalline state: structures of a symmetrical, cyclic hexamer and an 'opened-cube' octamer.

Six- and eight-membered hydrogen-bonded water clusters of novel structure types have been found in crystalline hydrates.

Synthesis and Characterization of Novel V/O/SO(4) Chains Incorporating 2,2'-Bipyridine Ligands: Crystal Structure of [V(2)O(2)(OH)(2)(SO(4))(2,2'-bpy)(2)].

The hydrothermal reaction of a mixture of vanadyl acetylacetonate (VO(acac)(2)), Na(2)SO(4), 2,2'-bipyridine (2,2'-bpy), and H(2)O for 48 h at 160 degrees C gives brown crystals of [V(2)O(2)(OH)(2)(SO(4))(2,2'-bpy)(2)] (1) in 70% yield. The structure of 1 consists of ribbons constructed from the infinite inorganic chains, [-{V(2)O(2)(OH)(2)}-&mgr;(2)-SO(4){V(2)O(2)(OH)(2)}-SO(4)](infinity), incorporating organic (2,2'-bipyridine) ligands. The inorganic chains are composed of the pairs of edge-sharing octahedra joined by {SO(4)} tetrahedra through octahedral-tetrahedral corner sharing.

[M V O (H O) (XO )]⋅24 H O (M=Fe, Co; X=V, S): Metal Oxide Based Framework Materials Composed of Polyoxovanadate Clusters.

New framework materials composed of well-defined vanadium oxide clusters were prepared by low-temperature reactions and characterized by X-ray crystal structure analysis. The structures of these solids contain {V O } cages linked into two interpenetrating three-dimensional networks by bridging {M(H O) } groups (M=Fe , Co ; see picture).