The Dimeric [V2O4F6]4– Vanadium Oxide‐Fluoride Anion in Na2(M(H2O)2)(V2O4F6) (M = Co2+, Ni2+, and Cu2+)

Donakowski, Martin D.; Vinokur, Anastasiya I.; Poeppelmeier, Kenneth R.

doi:10.1002/zaac.201200121

Cited by 9 publications

(7 citation statements)

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“…This is consistent with hard/soft acid/base interactions that have been previously observed and discussed. 9 , 23 , 24 , 45 − 49 …”

Section: Discussionmentioning

confidence: 99%

Syntheses of Two Vanadium Oxide–Fluoride Materials That Differ in Phase Matchability

Donakowski

Gautier²,

et al. 2014

Inorg. Chem.

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The syntheses of two noncentrosymmetric (NCS) vanadium oxide–fluoride compounds that originate from the same synthetic reagent concentrations are presented. Hydrothermal and low-temperature syntheses allow the isolation of metastable products that may form new phases (or decompose) upon heating and allow creation of chemically similar but structurally different materials. NCS materials synthesis has been a long-standing goal in inorganic chemistry: in this article, we compare two chemically similar NCS inorganic materials, NaVOF4(H2O) (I) and NaVO2–xF2+x (II; x = 1/3). These materials originate from the same, identical reagent mixtures but are synthesized at different temperatures: 100 °C and 150 °C, respectively. Compound I crystallizes in Pna21: a = 9.9595(4) Å, b = 9.4423(3) Å, and c = 4.8186(2) Å. Compound II crystallizes in P21: a = 6.3742(3) Å, b = 3.5963(2) Å, c = 14.3641(7) Å, and β = 110.787(3)°. Both materials display second-harmonic-generation activity; however, compound I is type 1 non-phase-matchable, whereas compound II is type 1 phase-matchable.

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“…This is consistent with hard/soft acid/base interactions that have been previously observed and discussed. 9 , 23 , 24 , 45 − 49 …”

Section: Discussionmentioning

confidence: 99%

Syntheses of Two Vanadium Oxide–Fluoride Materials That Differ in Phase Matchability

Donakowski

Gautier²,

et al. 2014

Inorg. Chem.

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“…The use of a second metal cation to further stabilize a framework structure for ion insertion has been previously employed. ,, Within oxide-fluoride chemistry, a second metal can be used to drive the ordering of oxide and fluoride anions as understood by the use of hard and soft properties. − Multiple different (either chemically and/or crystallographically) cation sites inside an oxide-fluoride can be created using early transition metals that favor different bonding environments which decidedly order the anion sites as either an oxide or a fluoride anion coordination. This was recently demonstrated with syntheses of Na 1.5 Ag 1.5 MO 3 F 3 (M = Mo, W); the sodium and silver ions differ sufficiently in their free ion polarizabilities to order the early transition metal oxide-fluorides. ,,, …”

Section: Introductionmentioning

confidence: 99%

AgNa(VO₂F₂)₂: A Trioxovanadium Fluoride with Unconventional Electrochemical Properties

et al. 2013

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We present structural and electrochemical analyses of a new double-wolframite compound: AgNa(VO2F2)2 or SSVOF. SSVOF is fully ordered and displays electrochemical characteristics that give insight into electrode design for energy storage beyond lithium-ion chemistries. The compound contains trioxovanadium fluoride octahedra that combine to form one-dimensional chain-like basic building units, characteristic of wolframite (NaWO4). The 1D chains are stacked to create 2D layers; the cations Ag(+) and Na(+) lie between these layers. The vanadium oxide-fluoride octahedra are ordered by the use of cations (Ag(+), Na(+)) that differ in polarizability. In the case of sodium-ion batteries, thermodynamically, the use of a sodium anode introduces a 300 mV loss in overall cell voltage as compared to a lithium anode; however, this can be counter-balanced by introduction of fluoride into the framework to raise the reduction potentials via an inductive effect. This allows sodium-ion batteries to have comparable voltages to lithium systems. With SSVOF as a baseline compound, we have identified new materials design rules for emerging sodium-ion systems that do not apply to lithium-ion systems. These strategies can be applied broadly to provide materials of interest for fundamental structural chemistry and appreciable voltages for sodium-ion electrochemistry.

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“…For the VOF 5 2À anion, the V O bond length is typically $ 1.60 Å , while V-F trans and V-F eq lengths are typically about 2.10 and 1.80 Å , respectively (Gautier et al, 2015). The dioxo vanadium fluoride anion has been observed as an ordered dimeric 2+ and Cu 2+ ) with the V1-O1 and V1-O2 distances of 1.606-1.627 and 1.664-1.702 Å , respectively (Donakowski et al, 2012b). The V-O distance in cis-dioxo vanadium fluoride of the ordered K 2 VO 2 F 3 is 1.636 Å and the terminal V-F distances are 1.862 and 1.914 Å (Ryan et al, 1971).…”

Section: Figurementioning

confidence: 99%

Orientational disorder and phase transitions in ammonium oxofluorovanadates, (NH₄)₃VOF₅ and (NH₄)₃VO₂F₄

Udovenko

Pogorel’tsev

Marchenko

et al. 2017

Acta Crystallogr Sect B

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Single crystals of (NH 4 ) 3 VOF 5 and (NH 4 ) 3 VO 2 F 4 were obtained from aqueous fluoride solutions and phase transitions in these compounds were investigated using X-ray diffraction, differential scanning microcalorimetry (DSM) and vibrational spectroscopy. The room-temperature (RT) phases of these compounds belong to orthorhombic symmetry [Immm and I222, Z = 6, for (NH 4 ) 3 VOF 5 and (NH 4 ) 3 VO 2 F 4 , respectively] with similar unit-cell parameters and two independent vanadium atoms. Above RT [at 350 and 440 K for (NH 4 ) 3 VOF 5 and (NH 4 ) 3 VO 2 F 4 , respectively], the compounds undergo reversible phase transitions into high-symmetry dynamically disordered elpasolite-like (Fm " 3 3m, Z = 4) structures with six and 12 spatial orientations of the vanadium octahedron for (NH 4 ) 3 VOF 5 and (NH 4 ) 3 VO 2 F 4 , respectively. The ligand atoms are distributed in a mixed (split) position of 24e + 96j, one of the ammonium groups is disordered on the tetrahedron 32f site, but another one forms eight spatial orientations due to disorder of its hydrogen atoms in the 96j position. DSM and spectroscopic data enable the phase transition from high temperature to room temperature to be connected with the transition from isotropic orientations of the octahedron to its two different dynamic states.

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The Dimeric [V₂O₄F₆]^4– Vanadium Oxide‐Fluoride Anion in Na₂(M(H₂O)₂)(V₂O₄F₆) (M = Co²⁺, Ni²⁺, and Cu²⁺)

Cited by 9 publications

References 46 publications

Syntheses of Two Vanadium Oxide–Fluoride Materials That Differ in Phase Matchability

Syntheses of Two Vanadium Oxide–Fluoride Materials That Differ in Phase Matchability

AgNa(VO₂F₂)₂: A Trioxovanadium Fluoride with Unconventional Electrochemical Properties

Orientational disorder and phase transitions in ammonium oxofluorovanadates, (NH₄)₃VOF₅ and (NH₄)₃VO₂F₄

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The Dimeric [V2O4F6]4– Vanadium Oxide‐Fluoride Anion in Na2(M(H2O)2)(V2O4F6) (M = Co2+, Ni2+, and Cu2+)

Cited by 9 publications

References 46 publications

Syntheses of Two Vanadium Oxide–Fluoride Materials That Differ in Phase Matchability

Syntheses of Two Vanadium Oxide–Fluoride Materials That Differ in Phase Matchability

AgNa(VO2F2)2: A Trioxovanadium Fluoride with Unconventional Electrochemical Properties

Orientational disorder and phase transitions in ammonium oxofluorovanadates, (NH4)3VOF5 and (NH4)3VO2F4

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The Dimeric [V₂O₄F₆]^4– Vanadium Oxide‐Fluoride Anion in Na₂(M(H₂O)₂)(V₂O₄F₆) (M = Co²⁺, Ni²⁺, and Cu²⁺)

AgNa(VO₂F₂)₂: A Trioxovanadium Fluoride with Unconventional Electrochemical Properties

Orientational disorder and phase transitions in ammonium oxofluorovanadates, (NH₄)₃VOF₅ and (NH₄)₃VO₂F₄