Hydrothermal synthesis of polyoxotungstate clusters, surface-modified with M(II)-organonitrogen subunits

R. Nandini Devi; Eric Burkholder; Jon A Zubieta

doi:10.1016/S0020-1693(02)01472-X

Hydrothermal synthesis of polyoxotungstate clusters, surface-modified with M(II)-organonitrogen subunits

R. Nandini Devi, Eric Burkholder, Jon A Zubieta

Department of Chemistry

Research output: Contribution to journal › Article

92 Scopus citations

Abstract

The hydrothermal reactions of Na₂WO₄·2H₂O with secondary metal cation sources in the presence of an appropriate organonitrogen donor yield a series of molecular clusters. The compounds [Ni(bpy)₃]_1.5[Ni(bpy)₂(H₂O){H ₃W₁₂O₄₀}]·0.5H₂O (1·0.5H₂O), [{Ni(phen)₂(H₂O)}₂{H₄W ₁₂O₄₀}]·4H₂O (2.4H₂O) and [{Cu(phen)₂}₄{H₂W₁₂O ₄₀}] [{Cu(phen)₂}₂{H₂W₁₂O ₄₀}]·3H₂O (4.3H₂O) are constructed from the α-metatungstate cluster [H₂W₁₂O₄₀]^6- core, covalently linked through oxo-bridges to secondary metal-organonitrogen ligand subunits. In the case of 1, the tungstate cluster is decorated by a single {Ni(bpy)₂(H₂O)}²⁺ subunit yielding an anionic bimetallic cluster, while in 2, two {Ni(phen)₂(H₂O)}²⁺ moieties are linked to the tungstate core to form a neutral bimetallic cluster. It is noteworthy that 4 is constructed of a cationic cluster, exhibiting a central tungstate core linked to four {Cu(phen)₂}²⁺ units, and an anionic bimetallic polyoxoanion, featuring a tungstate core bonded to two {Cu(phen)₂}²⁺ moieties. Compound 3, [{Cu(bpy)₂}₂W₁₀O₃₂]·2H ₂O (3.2H₂O) consists of two {Cu(bpy)₂}²⁺ subunits linked to the opposite sides of a decatungstate cluster, while compound 5 contains {Co(bpy)₃}³⁺ cations and the common Keggin anion, [CoW₁₂O₄₀]^6-.

Original language	English (US)
Pages (from-to)	150-156
Number of pages	7
Journal	Inorganica Chimica Acta
Volume	348
DOIs	https://doi.org/10.1016/S0020-1693(02)01472-X
State	Published - May 15 2003

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Keywords

Bimetallic oxide clusters
Copper tungstate
Hydrothermal synthesis
Nickel tungstate
Polyoxotungstates

ASJC Scopus subject areas

Biochemistry
Inorganic Chemistry
Physical and Theoretical Chemistry
Materials Chemistry

Cite this

Devi, R. N., Burkholder, E., & Zubieta, J. A. (2003). Hydrothermal synthesis of polyoxotungstate clusters, surface-modified with M(II)-organonitrogen subunits. Inorganica Chimica Acta, 348, 150-156. https://doi.org/10.1016/S0020-1693(02)01472-X

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title = "Hydrothermal synthesis of polyoxotungstate clusters, surface-modified with M(II)-organonitrogen subunits",

abstract = "The hydrothermal reactions of Na2WO4·2H2O with secondary metal cation sources in the presence of an appropriate organonitrogen donor yield a series of molecular clusters. The compounds [Ni(bpy)3]1.5[Ni(bpy)2(H2O){H 3W12O40}]·0.5H2O (1·0.5H2O), [{Ni(phen)2(H2O)}2{H4W 12O40}]·4H2O (2.4H2O) and [{Cu(phen)2}4{H2W12O 40}] [{Cu(phen)2}2{H2W12O 40}]·3H2O (4.3H2O) are constructed from the α-metatungstate cluster [H2W12O40]6- core, covalently linked through oxo-bridges to secondary metal-organonitrogen ligand subunits. In the case of 1, the tungstate cluster is decorated by a single {Ni(bpy)2(H2O)}2+ subunit yielding an anionic bimetallic cluster, while in 2, two {Ni(phen)2(H2O)}2+ moieties are linked to the tungstate core to form a neutral bimetallic cluster. It is noteworthy that 4 is constructed of a cationic cluster, exhibiting a central tungstate core linked to four {Cu(phen)2}2+ units, and an anionic bimetallic polyoxoanion, featuring a tungstate core bonded to two {Cu(phen)2}2+ moieties. Compound 3, [{Cu(bpy)2}2W10O32]·2H 2O (3.2H2O) consists of two {Cu(bpy)2}2+ subunits linked to the opposite sides of a decatungstate cluster, while compound 5 contains {Co(bpy)3}3+ cations and the common Keggin anion, [CoW12O40]6-.",

keywords = "Bimetallic oxide clusters, Copper tungstate, Hydrothermal synthesis, Nickel tungstate, Polyoxotungstates",

author = "Devi, {R. Nandini} and Eric Burkholder and Zubieta, {Jon A}",

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T1 - Hydrothermal synthesis of polyoxotungstate clusters, surface-modified with M(II)-organonitrogen subunits

AU - Devi, R. Nandini

AU - Burkholder, Eric

AU - Zubieta, Jon A

PY - 2003/5/15

Y1 - 2003/5/15

N2 - The hydrothermal reactions of Na2WO4·2H2O with secondary metal cation sources in the presence of an appropriate organonitrogen donor yield a series of molecular clusters. The compounds [Ni(bpy)3]1.5[Ni(bpy)2(H2O){H 3W12O40}]·0.5H2O (1·0.5H2O), [{Ni(phen)2(H2O)}2{H4W 12O40}]·4H2O (2.4H2O) and [{Cu(phen)2}4{H2W12O 40}] [{Cu(phen)2}2{H2W12O 40}]·3H2O (4.3H2O) are constructed from the α-metatungstate cluster [H2W12O40]6- core, covalently linked through oxo-bridges to secondary metal-organonitrogen ligand subunits. In the case of 1, the tungstate cluster is decorated by a single {Ni(bpy)2(H2O)}2+ subunit yielding an anionic bimetallic cluster, while in 2, two {Ni(phen)2(H2O)}2+ moieties are linked to the tungstate core to form a neutral bimetallic cluster. It is noteworthy that 4 is constructed of a cationic cluster, exhibiting a central tungstate core linked to four {Cu(phen)2}2+ units, and an anionic bimetallic polyoxoanion, featuring a tungstate core bonded to two {Cu(phen)2}2+ moieties. Compound 3, [{Cu(bpy)2}2W10O32]·2H 2O (3.2H2O) consists of two {Cu(bpy)2}2+ subunits linked to the opposite sides of a decatungstate cluster, while compound 5 contains {Co(bpy)3}3+ cations and the common Keggin anion, [CoW12O40]6-.

AB - The hydrothermal reactions of Na2WO4·2H2O with secondary metal cation sources in the presence of an appropriate organonitrogen donor yield a series of molecular clusters. The compounds [Ni(bpy)3]1.5[Ni(bpy)2(H2O){H 3W12O40}]·0.5H2O (1·0.5H2O), [{Ni(phen)2(H2O)}2{H4W 12O40}]·4H2O (2.4H2O) and [{Cu(phen)2}4{H2W12O 40}] [{Cu(phen)2}2{H2W12O 40}]·3H2O (4.3H2O) are constructed from the α-metatungstate cluster [H2W12O40]6- core, covalently linked through oxo-bridges to secondary metal-organonitrogen ligand subunits. In the case of 1, the tungstate cluster is decorated by a single {Ni(bpy)2(H2O)}2+ subunit yielding an anionic bimetallic cluster, while in 2, two {Ni(phen)2(H2O)}2+ moieties are linked to the tungstate core to form a neutral bimetallic cluster. It is noteworthy that 4 is constructed of a cationic cluster, exhibiting a central tungstate core linked to four {Cu(phen)2}2+ units, and an anionic bimetallic polyoxoanion, featuring a tungstate core bonded to two {Cu(phen)2}2+ moieties. Compound 3, [{Cu(bpy)2}2W10O32]·2H 2O (3.2H2O) consists of two {Cu(bpy)2}2+ subunits linked to the opposite sides of a decatungstate cluster, while compound 5 contains {Co(bpy)3}3+ cations and the common Keggin anion, [CoW12O40]6-.

KW - Bimetallic oxide clusters

KW - Copper tungstate

KW - Hydrothermal synthesis

KW - Nickel tungstate

KW - Polyoxotungstates

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JO - Inorganica Chimica Acta

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10.1016/S0020-1693(02)01472-X