Coordination capacity of Keggin anions as polytopic ligands: case study of [VNb12O40]15−

Mukhacheva, Anna A.; Volcheck, Victoria V.; Sheven, D. G.; Yanshole, Vadim V.; Kompankov, Nikolay B.; Haouas, Mohamed; Abramov, Pavel A.; Sokolov, Maxim N.

doi:10.1039/d1dt00765c

Cited by 6 publications

(5 citation statements)

References 37 publications

(33 reference statements)

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“…HPCL-ICP-AES hyphenated technique [ 34 ] is a powerful tool to study the reactivity/stability/evolution of different polyoxometalates in aqueous and organic solutions [ 35 , 36 , 37 ]. In the present research, this technique was a good complement for NMR-relaxation studies.…”

Section: Resultsmentioning

confidence: 99%

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NMR-Relaxometric Investigation of Mn(II)-Doped Polyoxometalates in Aqueous Solutions

Korenev

Burilova

Volchek

et al. 2023

IJMS

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Solution behavior of K;5[(Mn(H2O))PW11O39]·7H2O (1), Na3.66(NH4)4.74H3.1[(MnII(H2O))2.75(WO(H2O))0.25(α-B-SbW9O33)2]·27H2O (2), and Na4.6H3.4[(MnII(H2O)3)2(WO2)2(β-B-TeW9O33)2]·19H2O (3) was studied with NMR-relaxometry and HPLC-ICP-AES (High Performance Liquid Chromatography coupled with Inductively Coupled Plasma Atomic Emission Spectroscopy). According to the data, the [(Mn(H2O))PW11O39]5− Keggin-type anion is the most stable in water among the tested complexes, even in the presence of ethylenediaminetetraacetic acid (EDTA) or diethylenetriaminepentaacetic acid (DTPA). Aqueous solutions of 2 and 3 anions are less stable and contain other species resulting from dissociation of Mn2+. Quantum chemical calculations show the change in Mn2+ electronic state between [Mn(H2O)6]2+ and [(Mn(H2O))PW11O39]5−.

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Section: Resultsmentioning

confidence: 99%

“…they have a charge transfer character (at 2.198 eV), a delocalization character (at 2.601 eV), and a local excitation character (at 3.625 eV). [34] is a powerful tool to study the reactivity/stability/evolution of different polyoxometalates in aqueous and organic solutions [35][36][37].…”

Section: Quantum-chemical Calculations Of Mn 2+ Electronic Statesmentioning

confidence: 99%

NMR-Relaxometric Investigation of Mn(II)-Doped Polyoxometalates in Aqueous Solutions

Korenev

Burilova

Volchek

et al. 2023

IJMS

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“…Owing to the inherent lability of the coordination bonds connecting organometallic cations and POM anions, the organometallic fragments of organo–POMs exhibit dynamic behavior in solution. − They can pivot , on the surfaces of the POM or detach from the POM in response to external stimulisuch as solvents and temperaturewhile preserving the POM structure. This unique property, wherein the organometallic cation can dissociate from the POM, makes organo–POMs attractive as building blocks for synthesizing multimetallic-oxide clusters.…”

Section: Introductionmentioning

confidence: 99%

Reactivity of Organoiridium Tungsten Oxide Clusters with Transition Metal Aquo Cations

Sugiarto,

Mitsuhashi,

Sadakane

2024

Inorg. Chem.

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Organometallic−polyoxometalate (POM) complexes form a unique class of molecular organometallic oxides characterized by the dynamic behavior of the organometallic cations. Herein, we investigated the reactivity of Cp*Iroctatungstate clusters (where Cp* represents pentamethylcyclopentadienyl, C 5 Me 5 − ) with Werner-type transition-metal aquo cations. The addition of Ag + , Co 2+ , Ni 2+ , and M 3+ (M = Cr, Fe, or In) cations to the aqueous solution of Cp*Ir-octatungstate clusters resulted in the formation of [{Ag) 2 (M = Cr, 3-Cr; Fe, 3-Fe; or In, 3-In), respectively. All clusters share the same cubane-type {Cp*IrW 3 O 12 (OH)} 5− building block, representing the first examples of organoiridium-POMs functionalized by transition-metal aquo cations. These compounds are insoluble in water, facilitating the evaluation of their heterogeneous wateroxidation properties. Notably, 2-Co generates the highest catalytic water oxidation current. This work provides a new synthetic method to introduce metal−aquo complexes on an organometallic oxide cluster, producing multimetallic molecules that model the catalytic sites of complex oxides.

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“…The experimental results show that 1 exhibits good chemical stability, exceptional water vapor adsorption, and average proton conductivity. These findings suggest that the introduction of organodiphosphate into iso-PONbs is a feasible strategy for diversifying the PONb chemistry in not only the structural types but also the functions. , …”

Section: Introductionmentioning

confidence: 99%

An Organodiphosphate-Containing Polyoxoniobate Ring and Its Assembly into a Three-Dimensional Framework through Hydrogen Bonding

Cong,

Xiao,

Cai

et al. 2024

Inorg. Chem.

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In this work, a novel organodiphosphate-containing inorganic−organic hybrid polyoxoniobate (PONb) ring {(PO 3 CH 2 CH 2 PO 3 H) 4 Nb 8 O 16 } 4− (Nb 8 P 8 ) has been achieved by a one-pot hydrothermal method. The ring is constructed from a tetragonal {Nb 8 O 36 } motif and four {PO 3 CH 2 CH 2 PO 3 H} ligands. Interestingly, Nb 8 P 8 can be joined together via K−H 2 O clusters {K 2 (H 2 O) 4 (OH) 2 } to form one-dimensional chains {[K 2 (H 2 O) 4 (OH) 2 ]Nb 8 P 8 } n and further linked by {Cu(en) 2 } 2+ 1). 1 exhibits good chemical and thermal stability and has a high water vapor adsorption capacity of ≤224 cm 3 g −1 (22.71 mol•mol −1 ) at 298 K, outperforming most of the known polyoxometalate-based materials. Impedance measurements prove that 1 can transfer protons with moderate conductivity. This study not only contributes to the structural diversity of organodiphosphate-containing PONbs and PONb rings but also provides a reference for the development of PONb-based materials with unique performance.

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Coordination capacity of Keggin anions as polytopic ligands: case study of [VNb₁₂O₄₀]¹⁵⁻

Abstract: [VNb12O40]15− polytopic ligand can coordinate to up to five {(C6H6)Ru}2+ groups. Combined analytical separation tools together with 1H DOSY NMR were firstly applied to the solution studies of polyoxoniobate based complexes.

Cited by 6 publications

References 37 publications

NMR-Relaxometric Investigation of Mn(II)-Doped Polyoxometalates in Aqueous Solutions

NMR-Relaxometric Investigation of Mn(II)-Doped Polyoxometalates in Aqueous Solutions

Reactivity of Organoiridium Tungsten Oxide Clusters with Transition Metal Aquo Cations

An Organodiphosphate-Containing Polyoxoniobate Ring and Its Assembly into a Three-Dimensional Framework through Hydrogen Bonding

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