Supramolecular network of a framework material supported by the anion–π linkage of Keggin-type heteropolyoxotungstates: experimental and theoretical insights

A novel inorganic–organic hybrid has been synthesized and characterized. This hybrid contains a trinuclear Tb-organic cluster that is bound to three terminal oxygen atoms of the Keggin anion and sodium to form a discrete heterotetranuclear structure.

Oxygen Adsorption and Activation on Cobalt Center in Modified Keggin Anion-DFT Calculations

The influence of the cobalt cation geometric environment on catalytic activity, namely, oxygen adsorption and its activation, was investigated by exploring two groups of systems. The first group was formed by cobalt cation complexes, in which the Co2+ was surrounded by water-H2O or acetonitrile-CH3CN solvent molecules. This represents heteropolyacids salts (ConH3-nPW(Mo)12O40), where the Co2+ acts as a cation that compensates for the negative charge of the Keggin anion and is typically surrounded by solvent molecules in that system. The second group consisted of tungsten or molybdenum Keggin anions (H5PW11CoO39 and H5PMo11CoO39), having the Co2+ cation incorporated into the anion framework, in the position of one addenda atom. Detailed NOCV (Natural Orbitals for Chemical Valence) analysis showed that, for all studied systems, the σ-donation and σ-backdonation active channels of the electron transfer were responsible for the creation of a single Co-OO bond. Depending on the chemical/geometrical environment of the Co2+ cation, the different quantities of electrons were flown from the Co2+ 3d orbital to the π* antibonding molecular orbitals of the oxygen ligand, as well as in the opposite direction. In molybdenum and tungsten heteropolyacids, modified by Co2+ in the position of the addenda atom, activation of O2 was supported by a π-polarization process. Calculated data show that the oxygen molecule activation changed in the following order: H5PMo11CoO39 = H5PW11CoO39 > Co(CH3CN)52+ > Co(H2O)52+.

Synthesis, Characterization and Anti-Cancer Studies of Curcumin Diketimines-Heteropolyacid Composites

A novel composite of curcumin diketimine (CDK)-heteropolyacid (where HPA = vanadium doped Keggin anion and CDK = curcuminbenzoguanamine) had been synthesized. The hybrid composites were investigated by analytical methods such as elemental analysis, FTIR, 13C NMR, SEM, EDS, XRD, DSC-TGA, ESR spectral studies and biological activities. Encapsulated hybrid composite also studied (in vitro) against MCF-7 cancer cell lines. ESR results showed that the presence of (V4+) ion nitrogen ligation in the composite. 13C NMR of CDK ligand value of 183.37 and 55.06 ppm corresponds to (2=N) and (O-CH3) may be due to the composites. The morphology of molybdovanadate (HPA) showed a structure of self-assembled round shape of a diameter around 1 μm.

Bicapite, KNa2Mg2(H2PV145+O42)·25H2O, a new polyoxometalate mineral with a bicapped Keggin anion from the Pickett Corral mine, Montrose County, Colorado, U.S.A.

Bicapite, KNa2Mg2(H2PV145+O42)·25H2O, is a new mineral species (IMA2018-048) discovered at the Pickett Corral mine, Montrose County, Colorado, U.S.A. Bicapite occurs as square tablets up to about 0.2 mm on edge on montroseite-corvusite-bearing sandstone. Crystals are dark red-brown, often appearing black. The streak is orange, and the luster is vitreous. Bicapite is brittle, has a Mohs hardness of 1½, and displays one excellent cleavage on {100}. The measured density is 2.44(2) g/cm3. Bicapite is uniaxial (+), ω = 1.785(5), ε ≈ 1.81 (white light); pleochroism is red-brown; E > O, slight. The electron probe microanalysis and results of the crystal structure determination provided the empirical formula (based on 67 O apfu) (K1.23Na2.23Mg1.48)Σ4.94[H2.51P1.02(V13.915+Mo0.076+)Σ13.98O42]·25H2O. Bicapite is tetragonal, I4/m, with a = 11.5446(12) Å, c = 20.5460(14) Å, V = 2738.3(6) Å3, and Z = 2. The strongest four lines in the diffraction pattern are [d in Å (I) (hkl)]: 10.14 (100) (002,101); 2.978 (29) (134,206); 2.809 (11) (305); and 2.583 (11) (420,008). The atomic arrangement of bicapite was solved and refined to R1 = 0.0465 for 1008 independent reflections with I > 2σI. The structural unit is a [H2PV125+O40(V5+O)2]7– heteropolyanion composed of 12 distorted VO6 octahedra surrounding a central PO4 tetrahedron and capped on opposite sides by two VO5 square pyramids; the structural unit is a modification of the α-isomer of the Keggin anion, [XM12O40]n–. Charge balance in the structure is maintained by the [KNa2Mg2(H2O)25]7+ interstitial complex. The name bicapite is in recognition of this being the only known mineral with a structure based on a bicapped Keggin anion. The discovery of bicapite and numerous other natural polyoxometalate compounds in the Colorado Plateau uranium/vanadium deposits make that the most productive region found to date for naturally occurring polyoxometalate compounds.

Synthesis and Antibacterial Activity of Polyoxometalates with Different Structures

A new inorganic-organic hybrid compound, [{Cu(phen)2}2(H4W12O40)], was synthesized, and its crystal structure was determined. The Keggin anion H4W12O404− was grafted with two coordination units {Cu(phen)2}, forming an electrically neutral molecule. The antibacterial activity of several polyoxometalate compounds with different anionic structures including the new compound was studied. The results show that the compound 1 can inhibit the growth of Enterococcus faecalis FA2 strains and that antibacterial activity of the polyoxometalate compounds is dependent with component elements of POM but is less relative with the anion structures.

Comment on: “Synthesis of dodecamolybdoantimonate(v) salts containing the Keggin structure” by Raj P. Singh, Radheshyam P. Khatri, Jean Dubois, Sushma S. Gaur and Mitsuo Abe, J. Chem. Soc., Dalton Trans., 1990, 947–951

Instead of the claimed synthesis of M3[α-SbO4(Mo3O9)4]·nH2O (M = NH4, K, Rb, Cs) with Keggin anion, the authors simply prepared well-known hexagonal molybdenum oxide.

Combined HPLC-ICP-AES technique as an informative tool for the study of heteropolyniobates

This paper summarizes the application of the coupled HPLC-ICP-AES technique to study the substitution of niobium by tungsten in [Nb6O19]8− or [(OH)TeNb5O18]6− Lindqvist anions and the screening of mixed [PMo12−xNbxO40]n− Keggin anion formation.