Anion packing, hole filling, and HF solvation in A2(HF)nB12F12 and K2(HF)TiF6 (A=K, Cs)

Peryshkov, Dmitry V.; Friedemann, Roland; Goreshnik, Evgeny; Mazej, Zoran; Seppelt, Konrad; Strauss, Steven H.

doi:10.1016/j.jfluchem.2012.10.009

Cited by 16 publications

(12 citation statements)

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“…Since Na 3 (HF 2 )(TiF 6 ) (Na 3 HTiF 8 ) is known, the attempt was made to prepare the analogous potassium compound. Instead of the desired K 3 (HF 2 )(TiF 6 ), only a few single crystals of K 2 (HF)TiF 6 were grown from an n (KF): n (TiF 4 ) = 3:1 aHF solution. Vibrational bands that could be assigned to KHF 2 were also detected in the crystallization product by Raman spectroscopy.…”

Section: Resultsmentioning

confidence: 99%

“…Further crystallization of the synthesized hexafluoridotitanate(IV) salts led to single crystals of the corresponding A 2 TiF 6 phases and in the potassium case to the previously known solvated K 2 TiF 6 ·HF phase . Attempts to isolate the A 2 TiF 6 · n HF (A = Li, Na, Rb, Cs) compounds with coordinated HF molecules failed.…”

Section: Resultsmentioning

confidence: 99%

“…The possibility of incorporation of HF into a crystal structure by its coordination to metal centers and/or to fluorinated anions is known, and it was recently observed in the alkali metal fluoridotitanate(IV) compounds K 2 (HF)TiF 6 , K 4 [Ti 8 F 36 ]·8HF, and Rb 4 [Ti 8 F 36 ]·6HF . In almost all cases, HF molecules are coordinated to discrete fluorido anions.…”

Section: Introductionmentioning

confidence: 99%

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Increasing Structural Dimensionality of Alkali Metal Fluoridotitanates(IV)

2018

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Reactions between AF (A = Li, Na, K, Rb, Cs) and TiF (with starting n(AF):n(TiF) molar ratios in the range from 3:1 to 1:3) in anhydrous hydrogen fluoride yield [TiF], [TiF], [TiF], [TiF], and [TiF] salts. With the exception of the ATiF compounds, which consist of A cations and octahedral [TiF] anions, all of these materials arise from the condensation of TiF units. The anionic part in the crystal structures of A[TiF] (A = K, Cs) and A[TiF]·HF (A = Na, K, Rb) is composed of infinite ([TiF]) chains built of TiF octahedra sharing joint vertices. Each structure shows a slightly different geometry of the ([TiF]) chains. The crystal structure of Na[TiF]·HF is constructed from polymeric ([TiF]) anions that appear as two parallel infinite zigzag chains comprising TiF units, where each TiF unit of one chain is connected to a TiF unit of the other chain through a shared fluorine vertex. Slow decomposition of single crystals of K[TiF]·8HF and Rb[TiF]·6HF ( Shlyapnikov , I. M. ; et al. Chem. Commun. 2013 , 49 , 2703 ) leads to the formation of [TiF] (Rb) and [TiF] (K, Rb) salts. The former displays the same ([TiF]) double chain as in Na[TiF]·HF, while the anionic part in the latter, ([TiF]), represents the first example of a three-dimensional network built of TiF octahedra. The ([TiF]) anion was also found in [HO][TiF]. The crystal structure determination of Cs[TiF] revealed a new type of polymeric fluoridotitanate(IV) anion, ([TiF]). Similar to the ([TiF]) anion, it is also built of zigzag double chains comprising TiF units. However, in the former there are fewer connections between TiF units of two neighboring chains than in the latter.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Increasing Structural Dimensionality of Alkali Metal Fluoridotitanates(IV)

2018

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“…We are studying anhydrous, hydrated, solvated, and ligated metal ion salts of the icosahedral superweak anion B 12 F 12 2– (hereinafter Z 2– ). − The structures and other properties of M(H 2 O) n (Z) hydrates can serve as models for the hydration of alkaline earth and transition metal ions in solution − or in extended solids such as clays, − zeolites, , or metal–organic frameworks (MOFs). − The degree of hydration of an alkaline earth or transition metal compound can affect its electrical or proton conductivity, − its photoluminescence intensity, its fluorescence red-shift, or its ability to act as a UV filter, − among other physicochemical properties. The dehydration/rehydration behavior of M(H 2 O) n (Z) salts is especially important in light of the interest in thermodynamic and kinetic dehydration/rehydration studies of salt hydrates for the storage of low potential heat from solar energy. − Some salt hydrates are known to change their structure when D 2 O replaces H 2 O .…”

Section: Introductionmentioning

confidence: 99%

Manifestations of Weak O–H···F Hydrogen Bonding in M(H₂O)_n(B₁₂F₁₂) Salt Hydrates: Unusually Sharp Fourier Transform Infrared ν(OH) Bands and Latent Porosity (M = Mg–Ba, Co, Ni, Zn)

et al. 2018

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Eight M(H2O) n (Z) salt hydrates were characterized by single-crystal X-ray diffraction (Z2– = B12F12 2–): M = Ca, Sr, n = 7; M = Mg, Co, Ni, Zn, n = 6; M = Ba, n = 4, 5. Weak O–H···F hydrogen bonding between the M(H2O) n 2+ cations and Z2– resulted in room-temperature Fourier transform infrared (FTIR) spectra having sharp ν(OH) bands, with full widths at half max of 10–30 cm–1, which are much more narrow than ν(OH) bands in room temperature FTIR spectra of most salt hydrates. Clearly resolved νasym(OH/OD) and νsym(OH/OD) bands with Δν(OH) as small as 17 cm–1 and Δν(OD) as small as 11 cm–1 were observed (Δν(OX) = νasym(OX) – νsym(OX)). The isomorphic hexahydrates (R3̅) have two fac-(H2O)3 sets of H2O ligands and nearly octahedral coordination spheres. They exhibited four resolvable ν(OH) bands, one νasym(OH)/νsym(OH) pair for H2O ligands with longer O(H)···F distances and one νasym(OH)/νsym(OH) pair for H2O ligands with shorter O(H)···F distances. The ν(OH) bands for the three H2O molecules with shorter, slightly stronger O(H)···F hydrogen bonds were broader, more intense, and red-shifted by ca. 25 cm–1 relative to the bands for the three other H2O molecules, the first time that such small differences in relatively weak O(H)···F hydrogen bonds in the same crystalline hexahydrate have resulted in observable IR spectroscopic differences at room temperature. For the first time room temperature ν(OH) values for salt hexahydrates showed the monotonic progression Mg2+ > Co2+ > Ni2+ > Zn2+, essentially the same progression as the pK a values for these metal ions in aqueous solution. A further manifestation of the weak O–H···F hydrogen bonding in these hydrates is the latent porosity exhibited by Ba(H2O)5,8(Z), Sr(H2O) n,m (Z), and Ca(H2O)4,6(Z). Finally, the H2O/D2O exchange reaction Co(D2O)6(Z) → Co(H2O)6(Z) was ca. 50% complete in 1 h at 50 °C in N2/17 Torr H2O(g).

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“…For example, fluoroanions can be used to probe new bonding motifs in organometallic complexes, involving metals that include B [1], Co [2][3][4][5][6], Ga [7], As [1], Cd [8], Pd [9], In [7], Sn [10], and U [11]. One of the most intriguing properties of fluoroanion-containing materials is the ability to solvate HF, which has the potential to provide improved safety and efficiency for synthetic chemistry [7,[11][12][13][14][15][16][17][18][19][20][21][22][23][24][25][26][27][28]. For example, anhydrous HF-containing systems have great utility for synthesis of high oxidation state fluoroanions, such as [AgF 4 ]…”

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Iron Fluoroanions and Their Clusters by Electrospray Ionization of a Fluorinating Ionic Liquid

Zarzana

Groenewold

Benson

et al. 2015

J. Am. Soc. Mass Spectrom.

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Anion packing, hole filling, and HF solvation in A2(HF)nB12F12 and K2(HF)TiF6 (A=K, Cs)

Cited by 16 publications

References 40 publications

Increasing Structural Dimensionality of Alkali Metal Fluoridotitanates(IV)

Increasing Structural Dimensionality of Alkali Metal Fluoridotitanates(IV)

Manifestations of Weak O–H···F Hydrogen Bonding in M(H₂O)_n(B₁₂F₁₂) Salt Hydrates: Unusually Sharp Fourier Transform Infrared ν(OH) Bands and Latent Porosity (M = Mg–Ba, Co, Ni, Zn)

Iron Fluoroanions and Their Clusters by Electrospray Ionization of a Fluorinating Ionic Liquid

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Anion packing, hole filling, and HF solvation in A2(HF)nB12F12 and K2(HF)TiF6 (A=K, Cs)

Cited by 16 publications

References 40 publications

Increasing Structural Dimensionality of Alkali Metal Fluoridotitanates(IV)

Increasing Structural Dimensionality of Alkali Metal Fluoridotitanates(IV)

Manifestations of Weak O–H···F Hydrogen Bonding in M(H2O)n(B12F12) Salt Hydrates: Unusually Sharp Fourier Transform Infrared ν(OH) Bands and Latent Porosity (M = Mg–Ba, Co, Ni, Zn)

Iron Fluoroanions and Their Clusters by Electrospray Ionization of a Fluorinating Ionic Liquid

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Manifestations of Weak O–H···F Hydrogen Bonding in M(H₂O)_n(B₁₂F₁₂) Salt Hydrates: Unusually Sharp Fourier Transform Infrared ν(OH) Bands and Latent Porosity (M = Mg–Ba, Co, Ni, Zn)