Solvatothermal chemistry of organically-templated vanadium fluorides and oxyfluorides

Paul DeBurgomaster; Wayne Ouellette; Hongxue Liu; Charles J. O'Connor; Gordon T. Yee; Jon Zubieta

doi:10.1016/j.ica.2009.09.053

Solvatothermal chemistry of organically-templated vanadium fluorides and oxyfluorides

Paul DeBurgomaster, Wayne Ouellette, Hongxue Liu, Charles J. O'Connor, Gordon T. Yee, Jon Zubieta

Department of Chemistry

Research output: Contribution to journal › Article

17 Scopus citations

Abstract

The solvatothermal reactions of V₂O₅, the appropriate organoamine and HF in the temperature range 100-180 °C yielded a series of vanadium fluorides and oxyfluorides. The compounds [NH₄][H₃N(CH₂)₂NH₃][VF₆] (1) and [H₃N(CH₂)₂NH₃][VF₅(H₂O)] (2) contain mononuclear V(III) anions, while [H₃N(CH₂)₂NH₂(CH₂)₂NH₃]₂ [VF₅(H₂O)]₂[VOF₄(H₂O)] (3) exhibits both V(IV) and V(III) mononuclear anions. Both compound 4, [H₃NCH₂(C₆H₄)CH₂NH₃][VOF₄]·H₂O (4·H₂O) and compound 5, [HN(C₂H₄)₃NH][V₂O₂F₆ (H₂O)₂] (5) contain binuclear anions constructed from edge-sharing V(IV) octahedra. In contrast, [H₃N(CH₂)₂NH₂(CH₂)₂NH₃]₂[V₄O₄F₁₄(H₂O)₂], (6) exhibits a tetranuclear unit of edge- and corner-sharing V(IV) octahedra. Compound 7, [H₃N(CH₂)₂NH₂][VF₅], contains chains of corner-sharing {V^IVF₆} octahedra, while [H₂N(C₂H₄)₂NH₂]₃[V₄F₁₇O]·1.5H₂O (8·1.5H₂O) is two-dimensional with a layer of V(III) and V(IV) octahedra in an edge- and corner-sharing arrangement. In the case of [H₃N(CH₂)₂NH₃][V₂O₆] (9), there was no fluoride incorporation, and the {V₂ O₆}_n^{2 n -} anion is a one-dimensional chain of corner-sharing V(V) tetrahedra.

Original language	English (US)
Pages (from-to)	1102-1113
Number of pages	12
Journal	Inorganica Chimica Acta
Volume	363
Issue number	6
DOIs	https://doi.org/10.1016/j.ica.2009.09.053
State	Published - Apr 5 2010

Keywords

Solvatothermal synthesis
Vanadium fluorides
Vanadium oxyfluorides

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry
Materials Chemistry

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DeBurgomaster, P., Ouellette, W., Liu, H., O'Connor, C. J., Yee, G. T., & Zubieta, J. (2010). Solvatothermal chemistry of organically-templated vanadium fluorides and oxyfluorides. Inorganica Chimica Acta, 363(6), 1102-1113. https://doi.org/10.1016/j.ica.2009.09.053

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title = "Solvatothermal chemistry of organically-templated vanadium fluorides and oxyfluorides",

abstract = "The solvatothermal reactions of V2O5, the appropriate organoamine and HF in the temperature range 100-180 °C yielded a series of vanadium fluorides and oxyfluorides. The compounds [NH4][H3N(CH2)2NH3][VF6] (1) and [H3N(CH2)2NH3][VF5(H2O)] (2) contain mononuclear V(III) anions, while [H3N(CH2)2NH2(CH2)2NH3]2 [VF5(H2O)]2[VOF4(H2O)] (3) exhibits both V(IV) and V(III) mononuclear anions. Both compound 4, [H3NCH2(C6H4)CH2NH3][VOF4]·H2O (4·H2O) and compound 5, [HN(C2H4)3NH][V2O2F6 (H2O)2] (5) contain binuclear anions constructed from edge-sharing V(IV) octahedra. In contrast, [H3N(CH2)2NH2(CH2)2NH3]2[V4O4F14(H2O)2], (6) exhibits a tetranuclear unit of edge- and corner-sharing V(IV) octahedra. Compound 7, [H3N(CH2)2NH2][VF5], contains chains of corner-sharing {VIVF6} octahedra, while [H2N(C2H4)2NH2]3[V4F17O]·1.5H2O (8·1.5H2O) is two-dimensional with a layer of V(III) and V(IV) octahedra in an edge- and corner-sharing arrangement. In the case of [H3N(CH2)2NH3][V2O6] (9), there was no fluoride incorporation, and the {V2 O6}n2 n - anion is a one-dimensional chain of corner-sharing V(V) tetrahedra.",

keywords = "Solvatothermal synthesis, Vanadium fluorides, Vanadium oxyfluorides",

author = "Paul DeBurgomaster and Wayne Ouellette and Hongxue Liu and O'Connor, {Charles J.} and Yee, {Gordon T.} and Jon Zubieta",

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TY - JOUR

T1 - Solvatothermal chemistry of organically-templated vanadium fluorides and oxyfluorides

AU - DeBurgomaster, Paul

AU - Ouellette, Wayne

AU - Liu, Hongxue

AU - O'Connor, Charles J.

AU - Yee, Gordon T.

AU - Zubieta, Jon

PY - 2010/4/5

Y1 - 2010/4/5

N2 - The solvatothermal reactions of V2O5, the appropriate organoamine and HF in the temperature range 100-180 °C yielded a series of vanadium fluorides and oxyfluorides. The compounds [NH4][H3N(CH2)2NH3][VF6] (1) and [H3N(CH2)2NH3][VF5(H2O)] (2) contain mononuclear V(III) anions, while [H3N(CH2)2NH2(CH2)2NH3]2 [VF5(H2O)]2[VOF4(H2O)] (3) exhibits both V(IV) and V(III) mononuclear anions. Both compound 4, [H3NCH2(C6H4)CH2NH3][VOF4]·H2O (4·H2O) and compound 5, [HN(C2H4)3NH][V2O2F6 (H2O)2] (5) contain binuclear anions constructed from edge-sharing V(IV) octahedra. In contrast, [H3N(CH2)2NH2(CH2)2NH3]2[V4O4F14(H2O)2], (6) exhibits a tetranuclear unit of edge- and corner-sharing V(IV) octahedra. Compound 7, [H3N(CH2)2NH2][VF5], contains chains of corner-sharing {VIVF6} octahedra, while [H2N(C2H4)2NH2]3[V4F17O]·1.5H2O (8·1.5H2O) is two-dimensional with a layer of V(III) and V(IV) octahedra in an edge- and corner-sharing arrangement. In the case of [H3N(CH2)2NH3][V2O6] (9), there was no fluoride incorporation, and the {V2 O6}n2 n - anion is a one-dimensional chain of corner-sharing V(V) tetrahedra.

AB - The solvatothermal reactions of V2O5, the appropriate organoamine and HF in the temperature range 100-180 °C yielded a series of vanadium fluorides and oxyfluorides. The compounds [NH4][H3N(CH2)2NH3][VF6] (1) and [H3N(CH2)2NH3][VF5(H2O)] (2) contain mononuclear V(III) anions, while [H3N(CH2)2NH2(CH2)2NH3]2 [VF5(H2O)]2[VOF4(H2O)] (3) exhibits both V(IV) and V(III) mononuclear anions. Both compound 4, [H3NCH2(C6H4)CH2NH3][VOF4]·H2O (4·H2O) and compound 5, [HN(C2H4)3NH][V2O2F6 (H2O)2] (5) contain binuclear anions constructed from edge-sharing V(IV) octahedra. In contrast, [H3N(CH2)2NH2(CH2)2NH3]2[V4O4F14(H2O)2], (6) exhibits a tetranuclear unit of edge- and corner-sharing V(IV) octahedra. Compound 7, [H3N(CH2)2NH2][VF5], contains chains of corner-sharing {VIVF6} octahedra, while [H2N(C2H4)2NH2]3[V4F17O]·1.5H2O (8·1.5H2O) is two-dimensional with a layer of V(III) and V(IV) octahedra in an edge- and corner-sharing arrangement. In the case of [H3N(CH2)2NH3][V2O6] (9), there was no fluoride incorporation, and the {V2 O6}n2 n - anion is a one-dimensional chain of corner-sharing V(V) tetrahedra.

KW - Solvatothermal synthesis

KW - Vanadium fluorides

KW - Vanadium oxyfluorides

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