Isopolyoxometalates derived from arylstibonic acids with “reverse-Keggin ion” structures based on [M(RSb)12O28] cores, M = Co(ii) or Zn(ii)

Nicholson, Brian K.; Clark, C.J.; Telfer, Shane G.; Groutso, Tania

doi:10.1039/c2dt30341h

Cited by 18 publications

(7 citation statements)

References 21 publications

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“…may be used to chemically control the formed products. The results of this study can extend beyond anionic outer-sphere adsorption on an Al nanocluster to related systems that display similar structural features, such as polyoxoniobates, , reverse Keggins, − and heteroatom-substituted Keggins. , …”

Section: Introductionmentioning

confidence: 79%

Systematic Study of Aluminum Nanoclusters and Anion Adsorbates

et al. 2017

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The interactions between aqueous aluminum (Al) nanoclusters and ions in solution influence the reactivity of nanomaterials in natural waters and are crucial to the targeted syntheses of aluminum oxides. To contribute to the fundamental understanding of how both anion and Al-nanocluster properties affect the interactions, we carry out systematic modeling studies that employ density functional theory calculations embedded in a continuum solvent model. Energetic and electronic structure analysis is applied toward delineating the interactions of a range of probe adsorbate anions with Al nanoclusters to elucidate how small molecules may react with naturally occurring nanomaterials. The study spans seven small molecules on three model Al nanoclusters. Using this ion set, we correlate the size, shape, and formal charge of the adsorbate to the trends in adsorption energies. A key finding is that the collective effects of exposed oxygen functional groups, i.e., the distribution of functional groups, dictates the electrostatic potential of the nanocluster surface, which, in turn, controls trends in anion adsorption. The computed adsorption and deprotonation trends are correlated to known synthetic routes of Al-nanocluster formation and subsequent crystallization to give insight into the potential optimization of synthetic conditions.

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Section: Introductionmentioning

confidence: 79%

Systematic Study of Aluminum Nanoclusters and Anion Adsorbates

et al. 2017

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“…Recently, Winpenny’s group prepared a reverse Keggin ion comprising 12 {PhSb V } units in addenda positions and a central {M II O 4 } (M = Mn, Zn) group . The reactivity of organostibonic acids toward the formation of polyoxostibonates is also being intensively studied these days, and several representatives of POMs built exclusively by organoantimony units have already been obtained …”

Section: Introductionmentioning

confidence: 99%

Synthesis and Biological Activity of Organoantimony(III)-Containing Heteropolytungstates

et al. 2012

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Three discrete organoantimony(III)-containing heteropolytungstates [(PhSb(III))(4)(A-α-Ge(IV)W(9)O(34))(2)](12-) (1), [(PhSb(III))(4)(A-α-P(V)W(9)O(34))(2)](10-) (2), and [{2-(Me(2)NCH(2)C(6)H(4))Sb(III)}(3)(B-α-As(III)W(9)O(33))](3-) (3) have been synthesized in one-pot reactions in aqueous medium using the appropriate lacunary heteropolyanion precursor and organoantimony(III) source. Polyanions 1-3 were isolated as hydrated salts, (NH(4))(12)[(PhSb(III))(4)(A-α-Ge(IV)W(9)O(34))(2)]·20H(2)O (1a), Rb(9)Na[(PhSb(III))(4)(A-α-P(V)W(9)O(34))(2)]·20H(2)O (2a), and Rb(3)[{2-(Me(2)NCH(2)C(6)H(4))Sb(III)}(3)(B-α-As(III)W(9)O(33))]·7H(2)O (3a). The compounds 1a-3a were fully characterized in the solid state using infrared (IR) spectroscopy, single-crystal XRD, and thermogravimetric and elemental analyses. The stability of 1-3 in aqueous solution was confirmed by multinuclear NMR ((1)H, (13)C, (31)P, and (183)W) spectroscopy. Preliminary studies on the biological activity of 1-3 showed that all three compounds might act as potent antimicrobial agents.

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“…After cooling the reaction mixtured own to room temperature, Na 2 S 2 O 4 (0.087 g, 0.5 mmol) was added to the reaction mixture resulting to dark brown solution and the pH was adjusted to 2.0-2.5 by addition of 37 %H Cl followedb yacolor change to dark green. Thereaction mixture was filtered and the filtrate was left undisturbed to crystallize at 18 Method B: Thea bove synthetic procedure was repeated in the absence of Na 2 S 2 O 4 .The reaction mixture was filtered and the filtrate was left undisturbed to crystallize at 18 8 8C. Orange needles suitable for X-ray diffraction analysis were obtained after 1week.…”

Section: Methodsmentioning

confidence: 99%

“…[16] However,the only related d-Keggin structures observed so far are not POM anions but cationic species,f or example,t he {Al 13 } cation [17] and the "reverse-Keggin" ions incorporating either p-block elements (Sb 5+ )o rf irst row transition metal ions (Co 2+ ,Mn 2+ ,orZ n 2+ ). [18] Herein, we report the synthesis and characterization of the first members of the d-Keggin polyanionic polyoxometalate-based isomers to be isolated, compounds 1 and 2,with the general formula:T EAH p Na q [H 2 M 12 (XO 4 )O 33 (TEA)]•r H 2 O where p, q, r = [2, 3,8] for 1 and [4,1,4] for 2 [TEAH: C 6 H 16 NO 3 (N,Oatoms fully protonated);M :W VI 4 V V 8 ;X : V V ;T EA:C 6 H 13 NO 3 :h ydroxy groups fully deprotonated), respectively.The clusters were characterized in the solid state by X-ray diffraction and FT-IR analysis as well as in solution by electrospray ionization mass spectrometry (ESI-MS), UV/ Vis, and cyclic voltammetry.…”

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confidence: 99%

Trapping the δ Isomer of the Polyoxometalate‐Based Keggin Cluster with a Tripodal Ligand

et al. 2015

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rH2O where p, q, r = [2,3,8] for 1 and [4,1,4] Polyoxometalates (POMs) are anionic molecular metal oxides constructed from W, Mo, V or Nb. They attract much attention due to their structures, electronic properties [1] and applications in catalysis, [2] magnetism, [3] as well as medicine [4] and molecular electronics. [5] The first polyoxometalate compound was reported by Berzelius [6] in 1826 but it was not until the 1930s that the XRay structure of this iconic compound, the Keggin ion, was first elucidated. [6] This ion has a tetrahedral symmetry with the general formula [XM12O40] n-, where X is a heteroatom (P, Si, S, Ge, As, Co, Fe) [7] with four O atoms completing the tetrahedral geometry. Investigations of the Keggin structure revealed four additional isomers, each resulting from the 60 o rotation of the four basic {M3O13} units, giving α, β, γ, δ and ε isomers as reported by Baker and Figgis, see Figure 1. [8] With the α and β -isomers, the four building blocks are linked together in a corner-shared fashion, whilst in the case of γ, δ and ε the corner-shared linkages are replaced by one, three and six edge-shared, respectively. [9] Since the first report of the most common α-and β-Keggin isomers, [10] many researchers have investigated their properties, [11] whilst others reported families of transition metal substituted derivatives of α-, β-and γ-isomers. [12] The first Keggin species containing an ε-core was reported almost 60 years later as a Rh-substituted oxomolybdenum(V) complex, [13] followed by the report of a mixed-valence Mo(V)/Mo(VI) isopolyanion [14] , the La and Ni-substituted oxomolybdenum ε-Keggin isomers [15] and recently the Bi substituted vanadiumbased ε isomer [16] , respectively. However, the only related δ-Keggin structures observed so far are not POM anions but cationic species e.g. the {Al13} cation [17] and the "reverse-Keggin" ions incorporating either p-block elements (Sb 5+ ) or first row transition metal ions (Co 2+ , Mn 2+ or Zn 2+ ). [18] Herein, we report the synthesis and characterization of the first members of the δ-Keggin polyanionic isomers to be isolated, compounds 1 and 2, with the general formula: TEAHpNaq[H2M12(XO4)O33 ( Supporting information for this article is given via a link at the end of the document.

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Isopolyoxometalates derived from arylstibonic acids with “reverse-Keggin ion” structures based on [M(RSb)12O28] cores, M = Co(ii) or Zn(ii)

Cited by 18 publications

References 21 publications

Systematic Study of Aluminum Nanoclusters and Anion Adsorbates

Systematic Study of Aluminum Nanoclusters and Anion Adsorbates

Synthesis and Biological Activity of Organoantimony(III)-Containing Heteropolytungstates

Trapping the δ Isomer of the Polyoxometalate‐Based Keggin Cluster with a Tripodal Ligand

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