Metal-substituted tungstosulfates with Keggin structure: synthesis and characterization

Azuma, Shinya; Kadoguchi, Taiga; Eguchi, Yohei; Hirabaru, Hikaru; Ota, Hiromi; Sadakane, Masahiro; Yanagisawa, Kazumichi; Hasegawa, Tetsuya; Ueda, Tadaharu

doi:10.1039/c9dt04737a

Cited by 19 publications

(13 citation statements)

References 33 publications

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“…at more positive potentials as well as better catalysis than the corresponding phosphorus-and silicon-containing POMs. [172][173][174] Thus, by investigating the appropriate combinations of POMs, metal nanoparticles, polymers and electrodes, the sensitivity and selectivity could be considerably improved relative to those of reported methods, widening the analytical application range.…”

Section: Other Analytical Applicationsmentioning

confidence: 99%

Polyoxometalates in Analytical Sciences

Ueda

2020

ANAL. SCI.

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Polyoxometalates (POMs) have been used for spectrophotometric determinations of silicon and phosphorus under acidic conditions, referred to as the molybdenum yellow method and molybdenum blue method, respectively. Many POMs are redox active and exhibit fascinating but complicated voltammetric responses. These compounds can reversibly accommodate and release many electrons without exhibiting structural changes, implying that POMs can function as excellent mediators and can be applied to sensitive determination methods based on catalytic electrochemical reactions. In addition, some rare-earth-metal-incorporated POMs exhibit fluorescence, which enables sensitive determination by the enhancement and quenching of fluorescence intensities. In this review, various analytical applications of POMs are introduced, mainly focusing on papers published after 2000, except for the molybdenum yellow method and molybdenum blue method.

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Section: Other Analytical Applicationsmentioning

confidence: 99%

Polyoxometalates in Analytical Sciences

Ueda

2020

ANAL. SCI.

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“…Metal oxo clusters are finite polymetallic aggregates, among which a central M x O y core always plays an important role in the structure construction. Total hydrolysis of metal ions to obtain as large M x O y as possible and then termination via ligand protection could be a promising strategy toward high-nuclearity metal oxo clusters, as exemplified by polyoxometalates, , the first transition metal oxo clusters, − and lanthanide metal oxo clusters. , As for the main group of tin-oxo clusters (TOCs), they have attracted increasing research attention in the past 30 years because of their clear crystal structure for better understanding structure–property relationships and potential applications in the fields of catalysis, − extreme ultraviolet (EUV) lithography, − biomedicine, , and so on. To date, many types of TOCs such as the representative cube [ n -BuSn(O)O 2 P(C 6 H 11 ) 2 ] 4 , ladder [( n -BuSn(O)O 2 CR) 2 - n -BuSn(O 2 CR) 3 ] 2 (R = Ph, Me), drum [ n -BuSn(O)O 2 CC 5 H 9 ]·C 6 H 6 , and ball-like {(RSn) 12 O 14 (OH) 6 } 2+ (Sn 12 ) − clusters have been reported.…”

Section: Introductionmentioning

confidence: 99%

Organic–Inorganic High-Valence Sn₁₈-oxo Clusters: Direct Utilization of an Inorganic Sn(IV) Source to Improve the Nuclearity and Electrocatalytic CO₂ Reduction Properties

Tian

Lü

et al. 2022

Inorg. Chem.

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The high-valence tin-oxo clusters are of great significance because of their structural diversity and potential applications in many fields, e.g., catalysis, extreme ultraviolet (EUV) lithography, and so on. The synthesis of high-nuclearity tin-oxo clusters remains a great challenge currently, since the key inorganic Sn x O y core with Sn 4+ ions could not be obtained only by the in situ Sn−C bond cleavage in organic tin sources. In this context, we synthesize three organic−inorganic hybrid Sn 18 -oxo clusters, [(BuSn) 12 Sn 6 (μ 3 -O) 20 (ba) 12 (PhPO 3 ) 4 ] (Bu = butyl, Hba = benzoic acid), [(BuSn) 12 Sn 6 (μ 3 -O) 20 (pmba, as well as one Sn 6 -oxo cluster [(BuSn) 6 (μ 3 -O) 2 (μ 2 -OH) 4 (pnba) 6 (PhPO 3 ) 2 ] (Sn 6 ) (Hpnba = p-nitrobenzoic acid) by combining an inorganic precursor (SnCl 4 ) with an organic one (butyltin hydroxide oxide). It is shown that an inorganic dicyclo-chain-like Sn 6 O 8 core encapsulated in a U-shaped dodecanuclear butyltin-oxo ring plays an important role in the construction of Sn 18 -oxo clusters and that the use of a ligand with an electron-withdrawing group reduces the nuclearity of clusters to Sn 6 . Moreover, electrocatalytic CO 2 reduction studies confirm that the electrocatalytic activities of the Sn 18 clusters are superior to those of the Sn 6 cluster, probably due to the hybrid organotin− inorganotin structures. Our work not only opens a new way for constructing high-nuclearity tin-oxo clusters but also is helpful in deeply revealing the structure−properties relationship of tin-oxo clusters.

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“…5,6 The controlled pH treatment of polyoxo species under strictly controlled conditions results in the formation of lacunary anions, which are formed by partial decomposition of their parent compounds. [7][8][9] These complexes have formally lost one M=O vertex and possess reactive cavities with high charge density around the defective region due to the negatively charged oxygen ligands. [7][8][9] The defective region can react with peripheral metal cations forming a new class of compounds known as transition-metalsubstituted polyoxotungstates, [M(L)XW11O39] q− (X = e.g.…”

Section: Introductionmentioning

confidence: 99%

“…[7][8][9] These complexes have formally lost one M=O vertex and possess reactive cavities with high charge density around the defective region due to the negatively charged oxygen ligands. [7][8][9] The defective region can react with peripheral metal cations forming a new class of compounds known as transition-metalsubstituted polyoxotungstates, [M(L)XW11O39] q− (X = e.g. P(V), Si(IV), L = H2O, DMSO, etc.…”

Section: Introductionmentioning

confidence: 99%

Structural and Electronic Properties of Aqueous Transition−Metal−Substituted Polyoxotungstates

Thompson

González-Cabaleiro

Vilà‐Nadal

2022

Preprint

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Polyoxometalates (POMs) are a discrete class of polyanionic metal−oxo aggregates with a large diversity of topologies, structural flexibility, and functionality at the nanoscale. Controlled base treatment of these compounds produces monolacunary polyanions that behave as multi−dentate ligands, generating a class of compounds known as transition metal substituted POMs. These compounds demonstrate excellent redox stability, making them are integral precursors for electrochemical processes. In this work, Density Functional Theory (DFT) calculations have been employed to systematically studied the accuracy of various exchange−correlation functions in describing the properties of transition−metal−substituted polyoxotungstates which are integral precursors for electrochemical processes. Molecular geometries were optimized using several generalized gradient approximations (GGA), hybrid, and long−range−corrected GGA (LC−GGA) with whom all agreed well with experimental crystallographic results. We report the standard reduction potentials, U0red vs NHE, for the pH−independent redox processes present in Keggin [M(H2O)PW11O39]5−; M = Mn(III/II), Fe(III/II), Co(III/II), and Ru(III/II)) anions calculated as a function of Hartree−Fock (HF) exchange and provide insight into the electronic properties controlling it.

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Metal-substituted tungstosulfates with Keggin structure: synthesis and characterization

Abstract: Simple synthetic procedures for accessing novel metal-substituted tungstosulfates [SMW11O39]4− (M = Mn2+, Co2+, Ni2+, and Cu2+) with Keggin-type structures were developed.

Cited by 19 publications

References 33 publications

Polyoxometalates in Analytical Sciences

Polyoxometalates in Analytical Sciences

Organic–Inorganic High-Valence Sn₁₈-oxo Clusters: Direct Utilization of an Inorganic Sn(IV) Source to Improve the Nuclearity and Electrocatalytic CO₂ Reduction Properties

Structural and Electronic Properties of Aqueous Transition−Metal−Substituted Polyoxotungstates

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Metal-substituted tungstosulfates with Keggin structure: synthesis and characterization

Abstract: Simple synthetic procedures for accessing novel metal-substituted tungstosulfates [SMW11O39]4− (M = Mn2+, Co2+, Ni2+, and Cu2+) with Keggin-type structures were developed.

Cited by 19 publications

References 33 publications

Polyoxometalates in Analytical Sciences

Polyoxometalates in Analytical Sciences

Organic–Inorganic High-Valence Sn18-oxo Clusters: Direct Utilization of an Inorganic Sn(IV) Source to Improve the Nuclearity and Electrocatalytic CO2 Reduction Properties

Structural and Electronic Properties of Aqueous Transition−Metal−Substituted Polyoxotungstates

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Organic–Inorganic High-Valence Sn₁₈-oxo Clusters: Direct Utilization of an Inorganic Sn(IV) Source to Improve the Nuclearity and Electrocatalytic CO₂ Reduction Properties