Coupling Solid-State NMR with GIPAW ab Initio Calculations in Metal Hydrides and Borohydrides

Franco, Federico; Baricco, Marcello; Chierotti, Michele R.; Gobetto, Roberto; Nervi, Carlo

doi:10.1021/jp3126895

Cited by 29 publications

(33 citation statements)

References 76 publications

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“…This value is quite close to the ones obtained for binary alkali and alkaline‐earth hydrides by both experiment and DFT calculations: +3.0, +3.7, +3.4, +4.5, +6.7, and +8.7 ppm for LiH, NaH, MgH 2 , CaH 2 , SrH 2 , and BaH 2 , respectively 40. 41 More complex ionic metal hydrates also show chemical shifts in a similar positive range, for example, +3 ppm for Ca 2 LiC 3 H,34 +5.1 and +6.1 ppm for the H − ion in the mayenites [Ca 24 Al 28 O 64 ] 4+ ⋅ 4 H − and [Sr 24 Al 28 O 64 ] 4+ ⋅ 4 H − ,42 respectively. It should be noted that the reference TMS was measured externally and thus, an error up to 1 ppm might be taken into account.…”

Section: Resultssupporting

confidence: 87%

Zintl‐Phase Sr₃LiAs₂H: Crystal Structure and Chemical Bonding Analysis by the Electron Localizability Approach

Feng

Prots

Bobnar

et al. 2015

Chemistry A European J

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The compound Sr3 LiAs2 H was synthesized by reaction of elemental strontium, lithium, and arsenic, as well as LiH as hydrogen source. The crystal structure was determined by single-crystal X-ray diffraction: space group Pnma; Pearson symbol oP28; a = 12.0340(7), b = 4.4698(2), c = 12.5907(5) Å; V = 677.2(1) Å(3) ; RF = 0.047 for 1021 reflections and with 36 parameters refined. The positions of the hydrogen atoms were first revealed by the electron localizability indicator and subsequently confirmed by crystal structure refinement. In the crystal structure of Sr3 LiAs2 H the metal atoms are arranged in a Gd3 NiSi2 -type motif, whereas the hydrogen atoms are arranged in a distorted tetrahedral environment formed by strontium. The calculated band structure revealed that Sr3 LiAs2 H is a semiconductor, which is in agreement with its diamagnetic behavior. Thus, Sr3 LiAs2 H is considered as a (charge-balanced) Zintl phase.

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Section: Resultssupporting

confidence: 87%

Zintl‐Phase Sr₃LiAs₂H: Crystal Structure and Chemical Bonding Analysis by the Electron Localizability Approach

Feng

Prots

Bobnar

et al. 2015

Chemistry A European J

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“…The Brillouin zones were automatically sampled with the MonkhorstPack scheme, 56 in a similar approach as previously described. 57 Geometry optimization, phonon and NMR chemical shift calculations for compounds 2A, 3A, 4A, 5A, 6A, 2B, 3B, 4B, 5B, 6B were performed with a grid mesh of 2×1×1, 2×2×2, 2×2×1, 3×2×1, 2×1×2, 1×2×1, 3×1×1, 3×1×1, and 3×1×1, respectively. For compounds 1A, and 1B grid meshes of 2×2×1 and 3×1×2 were respectively used.…”

Section: Amentioning

confidence: 99%

Natural Abundance ¹⁵N and ¹³C Solid‐State NMR Chemical Shifts: High Sensitivity Probes of the Halogen Bond Geometry

Vioglio

Catalano

Vasylyeva

et al. 2016

Chemistry A European J

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Solid-State Nuclear Magnetic Resonance (SSNMR) is a versatile characterization technique that can provide a plethora of information complementary to Single Crystal X-Ray Diffraction (SCXRD) analysis. However, the latter is still pivotal in assessing the halogen bond (XB) occurrence and having a rough estimation of its strength through the normalized distance parameter (RXB), obtained from experimental crystallographic data. Herein, we present an experimental and computational investigation of the relationship between the strength of an XB and the SSNMR chemical shifts of the nonquadrupolar nuclei either directly involved in the interaction ( 15 N) or covalently bonded to the halogen atom ( 13 C). We have prepared two series of X-bonded co-crystals based upon two different dipyridyl modules, and several halobenzenes and diiodoalkanes, as XB-donors. SCXRD structures of three novel co-crystals between 1,2-bis(4-pyridyl)ethane, and 1,4-diiodobenzene, 1,6-diiodododecafluorohexane, and 1,8-diiodohexadecafluorooctane are reported. For the first time, the change in the 15 N SSNMR chemical shifts upon XB formation is shown to experimentally correlate with the strength of the XB. The same overall trend is confirmed by density functional theory (DFT) calculations of the chemical shifts.13 C NQS experiments show a positive, linear correlation between the chemical shifts and the C-I elongation, which is an indirect probe of the strength of the XB. These correlations can be of general utility to estimate the strength of the XB occurring in diverse adducts by using affordable SSNMR analysis.In recent years, halogen bonding (XB) has been attracting increasing attention thanks to its applications in different fields, e.g., crystal engineering, materials chemistry, and biochemistry.1-3 The success of this specific noncovalent interaction derives from its unique physico-chemical properties, namely strength, selectivity, tunability, and directionality.4,5 XB spans an energy range similar to that of the more commonly used hydrogen bonding, i.e., 5-200 kJ/mol.6 By changing the XB-donor atom involved in the interaction or its covalently-bound substituents it is possible to fine-tune the final strength of the XB, an extremely useful feature for the design of new supramolecular species. 7 In addition, XB is strongly directional, 8,9 thus enabling the predictable alignment of molecular building blocks into crystalline architectures and functional materials, such as photoresponsive polymers, pharmaceutical co-crystals, porous materials, among others.10-14 XB plays also a key role in anion recognition and coordination both in solid state and in solution, 15,16 ability of relevant interest especially for biological systems. 17 The 2013 IUPAC XB definition states: "A halogen bond occurs when there is evidence of a net attractive interaction between an electrophilic region associated with a halogen atom in a molecular entity and a nucleophilic region in another, or the same, molecular entity". 18 The counterintuitive electrophilic b...

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“…We additionally examine this similarity by noting that in borohydrides like LiBH

_{4}

, KBH

_{4}

, and LiK(BH

_{4}

)

_{2}

, all the [BH

_{4}

]

^{-}

anions are rigid, nearly ideal tetrahedra centered at the position of B. Therefore, the detailed arrangement of the B atoms surrounding Li and/or K atoms may provide useful information for a discussion on the structure similarity . For this purpose, we computed the radial distribution

ρ_{l}

of the Li–B and K–B “bonds” lengths l for these compounds and show the results in the top panel of Fig.…”

Section: Thermodynamic Stabilitymentioning

confidence: 99%

First-principles prediction for the stability of LiK(BH4)2

Tuan

Nguyen

Huan

2014

Phys. Status Solidi B

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authoren Lithium/potassium borohydride LiK(BH4)2 was recently synthesized and reported to be in a Pnma phase at ambient conditions. Subsequent theoretical studies show that this phase is metastable at finite temperatures up to 400 K. Studying the Pnma phase of LiK(BH4)2 by first‐principles calculations, we show that this phase is dynamically stable. Although the Pnma phase is metastable at finite temperatures as reported by previous studies, we find that it can be significantly stabilized by compression. Based on the structural similarity between the reactant LiBH4 and the product LiK(BH4)2 of the synthesization reaction, we suggest that the formation of the Pnma phase of LiK(BH4)2 may be driven by the kinetic of the reaction, according to the empirical Ostwald's steps rule in crystal nucleation. Therefore, it may be interesting to explore other possible low‐energy phases of LiK(BH4)2 by recently developed structure prediction methods.

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Coupling Solid-State NMR with GIPAW ab Initio Calculations in Metal Hydrides and Borohydrides

Cited by 29 publications

References 76 publications

Zintl‐Phase Sr₃LiAs₂H: Crystal Structure and Chemical Bonding Analysis by the Electron Localizability Approach

Zintl‐Phase Sr₃LiAs₂H: Crystal Structure and Chemical Bonding Analysis by the Electron Localizability Approach

Natural Abundance ¹⁵N and ¹³C Solid‐State NMR Chemical Shifts: High Sensitivity Probes of the Halogen Bond Geometry

First-principles prediction for the stability of LiK(BH4)2

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Coupling Solid-State NMR with GIPAW ab Initio Calculations in Metal Hydrides and Borohydrides

Cited by 29 publications

References 76 publications

Zintl‐Phase Sr3LiAs2H: Crystal Structure and Chemical Bonding Analysis by the Electron Localizability Approach

Zintl‐Phase Sr3LiAs2H: Crystal Structure and Chemical Bonding Analysis by the Electron Localizability Approach

Natural Abundance 15N and 13C Solid‐State NMR Chemical Shifts: High Sensitivity Probes of the Halogen Bond Geometry

First-principles prediction for the stability of LiK(BH4)2

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Zintl‐Phase Sr₃LiAs₂H: Crystal Structure and Chemical Bonding Analysis by the Electron Localizability Approach

Zintl‐Phase Sr₃LiAs₂H: Crystal Structure and Chemical Bonding Analysis by the Electron Localizability Approach

Natural Abundance ¹⁵N and ¹³C Solid‐State NMR Chemical Shifts: High Sensitivity Probes of the Halogen Bond Geometry