The Anderson–Evans polyoxometalate: From inorganic building blocks via hybrid organic–inorganic structures to tomorrows “Bio-POM”

Naphthyl-Containing Organophosphonate Derivatives of Keggin-Type Polyoxotungstates

“…This question is yet to be experimentally confirmed as straightforward analogies with other monovacant Keggin-type species are usually unfeasible due to the peculiar behavior of borotungstates in aqueous solution when compared with isoelectronic species like [XW 11 O 39 ] 8´( X = Si, Ge). For example, the reaction of tungstate ions with [HBW 11 O 39 ] 8´d oes not directly lead to the plenary α-[BW 12 O 40 ] 5´K eggin ion. Instead, one ditungstate fragment places over the vacant site to lead to the [BW 13 O 46 H 3 ] 8ś pecies, which further condenses into oligomeric anions at lower pH values [51].…”

“…Stoichiometric reactions of the monolacunary Keggin-type anions [H n XW 11 O 39 ] 8´( X = B, n = 1; X = Si, n = 0) and 1-naphthylmethylphosphonic acid in acetonitrile were carried out with tetrabutylammonium (TBA) bromide as phase transfer agent to dissolve the POM cluster in the organic media. After an overnight reflux and filtering KBr and traces of unreacted POM precursor off, the crude products were obtained upon solvent removal under vacuum.…”

“…The original synthesis was carried out employing the [HBW 11 O 39 ] 8´a nion as POM precursor to evaluate whether lacunary heteropolytunsgtates with heteroatoms of the group 13 can act as inorganic platforms for their derivatization with p-block organo-groups. This question is yet to be experimentally confirmed as straightforward analogies with other monovacant Keggin-type species are usually unfeasible due to the peculiar behavior of borotungstates in aqueous solution when compared with isoelectronic species like [XW 11 O 39 ] 8´( X = Si, Ge).…”

“…We selected the [HBW 11 O 39 ] 8´a nion for our studies to determine whether borotungstates could be organically derivatized following this route in spite of its peculiar reactivity when compared with analogues that contain heteroatoms from groups 14 and 15, and we employed the isomorphic and topologically equivalent [SiW 11 O 39 ] 8´a s pattern in the reaction with 1-naphthylmethylphosphonic acid.…”

β,β-Isomer of Open-Wells–Dawson Polyoxometalate Containing a Tetra-Iron(III) Hydroxide Cluster: [{Fe4(H2O)(OH)5}(β,β-Si2W18O66)]9−

“…Polyoxometalates (POMs) are discrete metal oxide clusters that are of interest as soluble metal oxides, with applications in catalysis, medicine, and materials science [1][2][3][4][5][6][7][8][9][10][11][12][13]. Recently, the open-Wells-Dawson POMs have been an emerging class of POMs [14][15][16][17][18][19][20][21][22][23][24][25][26][27][28] [29].…”