K2B12F12: A rare A2X structure for an ionic compound at ambient conditions

Peryshkov, Dmitry V.; Strauss, Steven H.

doi:10.1016/j.jfluchem.2010.06.015

Cited by 24 publications

(39 citation statements)

References 28 publications

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“…Note that the corresponding changes calculated previously for the fluoride-substituted species are much smaller . The available experimental data for B 12 X 12 2– and B 12 H 11 X 2– with X = Cl, Br confirm these computed trends. − Tables S3 and S4 compare the shortest bond lengths of each of these bonds in chlorinated and brominated closo-dodeca-boranes with available experimental data.…”

Section: Resultssupporting

confidence: 64%

Theoretical Study of Halogenated B₁₂H_nX_(12–n)^2– (X = F, Cl, Br)

et al. 2019

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The closoborane and their derivatives have attracted high interest due to their superionic conductivity. Very recently, high ionic conductivities have been reported for compounds containing the closoborane ion B 12 H 12 2− . In this work, we address halogen-substituted ions B 12 H n X (12−n)2− (n = 0−3, 6, 9−12 and X = F, Cl, Br) using DFT calculations to probe the structures, the chemical stability, and the electrochemical stability, as well as spectroscopic properties in view of potential future applications. Considering the theoretical reaction n/12 B 12 H 12 2− + (12−n)/12 B 12 X 12 2− → B 12 H n X (12−n) 2− , it appears that for X = Cl and Br the compounds with n = 6 are stabilized by about 100 kJ/mol. The calculation of the vertical detachment energy (which is indirectly related to the electrochemical stability) shows an increasing stability with increasing halogen content. These results suggest that, for practical applications, it is likely that a partially halogenated ion offers the best compromise. The calculations of vibrational properties and NMR chemical shifts also reveal several systematic trends, which are discussed and compared to available literature values.

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Section: Resultssupporting

confidence: 64%

Theoretical Study of Halogenated B₁₂H_nX_(12–n)^2– (X = F, Cl, Br)

et al. 2019

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“…For example, this strategy was successful in greatly enhancing the Li + conductivity by 3 orders of magnitude in LiNH 2 via the substitution of Li + with Na + to form (Li 0.75 Na 0.25 )NH 2 . Another potential way to expand the K poly(carba)borate lattice to improve K + translational mobility is to alternatively use larger anions such as halogen-substituted CB 11 H 6 X 6 – or B 12 X 12 2– (X = F, Cl, Br, I), ,,− which will again ameliorate the interstitial bottlenecks. We are currently pursuing such strategies.…”

Section: Discussionmentioning

confidence: 99%

Structural and Dynamical Properties of Potassium Dodecahydro-monocarba-closo-dodecaborate: KCB₁₁H₁₂

Dimitrievska

Stavila

et al. 2020

J. Phys. Chem. C

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MCB 11 H 12 (M: Li, Na) dodecahydro-monocarba-closo-dodecaborate salt compounds are known to have stellar superionic Li + and Na + conductivities in their hightemperature disordered phases, making them potentially appealing electrolytes in all-solidstate batteries. Nonetheless, it is of keen interest to search for other related materials with similar conductivities while at the same time exhibiting even lower (more device-relevant) disordering temperatures, a key challenge for this class of materials. With this in mind, the unknown structural and dynamical properties of the heavier KCB 11 H 12 congener were investigated in detail by X-ray powder diffraction, differential scanning calorimetry, neutron vibrational spectroscopy, nuclear magnetic resonance, quasielastic neutron scattering, and AC impedance measurements. This salt indeed undergoes an entropy-driven, reversible, order−disorder transformation and with a lower onset temperature (348 K upon heating and 340 K upon cooling) in comparison to the lighter LiCB 11 H 12 and NaCB 11 H 12 analogues. The K + cations in both the low-T ordered monoclinic (P2 1 /c) and high-T disordered cubic (Fm3̅ m) structures occupy octahedral interstices formed by CB 11 H 12 − anions. In the low-T structure, the anions orient themselves so as to avoid close proximity between their highly electropositive C−H vertices and the neighboring K + cations. In the high-T structure, the anions are orientationally disordered, although to best avoid the K + cations, the anions likely orient themselves so that their C−H axes are aligned in one of eight possible directions along the body diagonals of the cubic unit cell. Across the transition, anion reorientational jump rates change from 6.2 × 10 6 s −1 in the low-T phase (332 K) to 2.6 × 10 10 s −1 in the high-T phase (341 K). In tandem, K + conductivity increases by about 30-fold across the transition, yielding a high-T phase value of 3.2 × 10 −4 S cm −1 at 361 K. However, this is still about 1 to 2 orders of magnitude lower than that observed for LiCB 11 H 12 and NaCB 11 H 12 , suggesting that the relatively larger K + cation is much more sterically hindered than Li + and Na + from diffusing through the anion lattice via the network of smaller interstitial sites.

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“…Selected interatomic distances and angles are listed in Table 1. The structure of the B 12 F 12 2-anion in this compound is normal, [1,[3][4][5][6] and it is also the most precise structure of any molecular B 12 species, with B-F and B-B esd values of 0.0005-0.0008 Å ( Figure S1). The anions are packed in a cubic close-packed (CCP)-like array, with a network of H 3 O + ions and H 2 O molecules intercalated between the parallel planes of the anions (Figure 1).…”

Section: Resultsmentioning

confidence: 89%

“…unanticipated compared to salts of B 12 H 12 2-, [8][9][10][11] B 12 Cl 12 2-, [12][13][14] B 12 (OH) 12 2-, [15,16] and B 12 (CH 3 ) 12 2- [17] on one hand, and of salts of typical fluoroanions, such as BF 4 -, PF 6 -, Sb 2 F 11 -, SiF 6 2-, and MnF 6 2-, on the other]. For example, K 2 B 12 H 12 exhibits a common antifluorite structure, [10] but K 2 B 12 F 12 exhibits an intermetallic Ni 2 In structure [3] (the B 12 centroids occupy the idealized hexagonal close-packed positions of the In atoms [18] ), which is the first time that this structure has been observed for an ionic compound with a polyatomic anion at ambient temperatures and pressures.…”

Section: Introductionmentioning

confidence: 99%

The Structure of (H₃O)₂B₁₂F₁₂·6H₂O – a CCP Lattice of B₁₂F₁₂^2– Anions Intercalated with a Nonplanar Network of O–H···O Connected O₆ Rings

et al. 2011

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Hydrates of the dihydronium salt of the superweak anion B12F122– have been synthesized and structurally characterized. The structure of (H3O)2B12F12·6H2O consists of a cubic close‐packed (CCP) array of B12F122– anions intercalated with nonplanar, infinite networks of O6 rings composed of H3O+ ions and H2O molecules. Similar to other salts of B12F122–, (H3O)2B12F12·6H2O exhibits rapid structural modification, termed latent porosity, and reversibly desorbswater to form other hydrate phases: (H3O)2B12F12·4H2O,(H3O)2B12F12·2H2O, and (H3O)2B12F12. (H3O)2B12F12·6H2O is another example of the weak coordinating properties of the B12F122– anion.

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K2B12F12: A rare A2X structure for an ionic compound at ambient conditions

Cited by 24 publications

References 28 publications

Theoretical Study of Halogenated B₁₂H_nX_(12–n)^2– (X = F, Cl, Br)

Theoretical Study of Halogenated B₁₂H_nX_(12–n)^2– (X = F, Cl, Br)

Structural and Dynamical Properties of Potassium Dodecahydro-monocarba-closo-dodecaborate: KCB₁₁H₁₂

The Structure of (H₃O)₂B₁₂F₁₂·6H₂O – a CCP Lattice of B₁₂F₁₂^2– Anions Intercalated with a Nonplanar Network of O–H···O Connected O₆ Rings

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K2B12F12: A rare A2X structure for an ionic compound at ambient conditions

Cited by 24 publications

References 28 publications

Theoretical Study of Halogenated B12HnX(12–n)2– (X = F, Cl, Br)

Theoretical Study of Halogenated B12HnX(12–n)2– (X = F, Cl, Br)

Structural and Dynamical Properties of Potassium Dodecahydro-monocarba-closo-dodecaborate: KCB11H12

The Structure of (H3O)2B12F12·6H2O – a CCP Lattice of B12F122– Anions Intercalated with a Nonplanar Network of O–H···O Connected O6 Rings

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Theoretical Study of Halogenated B₁₂H_nX_(12–n)^2– (X = F, Cl, Br)

Theoretical Study of Halogenated B₁₂H_nX_(12–n)^2– (X = F, Cl, Br)

Structural and Dynamical Properties of Potassium Dodecahydro-monocarba-closo-dodecaborate: KCB₁₁H₁₂

The Structure of (H₃O)₂B₁₂F₁₂·6H₂O – a CCP Lattice of B₁₂F₁₂^2– Anions Intercalated with a Nonplanar Network of O–H···O Connected O₆ Rings