31P chemical shifts in BP, GaP and InP

Humphries, Leroy J.; Sears, R. E. J.

doi:10.1016/0022-3697(75)90058-x

Cited by 12 publications

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References 9 publications

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“…The 31 P signals are shifted slightly more to lower fields than in Li 3 AlP 2 . The small signal at −143 ppm can be assigned to GaP . Summing up, the NMR measurements are in very good agreement with the crystal structure evaluation on the basis of the Rietveld analyses.…”

Section: Resultssupporting

confidence: 81%

Synthesis, Structure, Solid‐State NMR Spectroscopy, and Electronic Structures of the Phosphidotrielates Li₃AlP₂ and Li₃GaP₂

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Raudaschl‐Sieber

et al. 2020

Chemistry A European J

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Thel ithium phosphidoaluminate Li 9 AlP 4 represents apromising new compound with ahigh lithium ion mobility. This triggered the searchf or new members in the familyo f lithium phosphidotrielates, and the novel compounds Li 3 AlP 2 and Li 3 GaP 2 ,o btained directly from the elements via ball milling ands ubsequenta nnealing, are reported here. It was unexpectedly found through band structure calculations that Li 3 AlP 2 and Li 3 GaP 2 are directb and gap semiconductors with band gaps of 3.1 and 2.8 eV,r espectively.R ietveld anal-yses revealt hat both compounds crystallize isotypically in the orthorhombic space group Cmce (no. 64) with lattice parameters of a = 11.5138(2), b = 11.7634(2)a nd c = 5.8202(1) for Li 3 AlP 2 ,a nd a = 11.5839(2), b = 11.7809(2) and c = 5.8129(2) for Li 3 GaP 2 .T he crystal structures feature TrP 4 (Tr = Al, Ga) corner-and edge-sharing tetrahedra, forming two-dimensional 1 2 TrP 2 3À ½ layers. The lithium atoms are located between and inside these layers. The crystal structures were confirmed by MAS-NMR spectroscopy.Li 2 SiP 2 . [8,11] Interestingly,t he phases Li 8 SiP 4 ,L i 5 SiP 3 (= Li 10 Si 2 P 6 ), Li 2 SiP 2 ,a nd LiSi 2 P 3 are connected by af ormal reduction of the formula by units of Li 3 P. [11] Al ower Li 3 Pc ontent leads to a higherc onnectivity of the tetrahedra.Compared to the related sulfide-basedl ithium ion conductors, [3,6,7,12] the anionic substructure of phosphido-based conductorsc arry one additional charge( formal "P 3À "v ersus a formal "S 2À "), and thus the Li content that is required for chargeb alance is higher.R ecently,w ee xpanded this concept of highly charged tetrahedra to lithium phosphidoaluminates by replacing the centralg roup 14 metal by aluminium. [13] Li 9 AlP 4 contains highly charged[TrP 4 ] 9À tetrahedra andreaches high ionic conductivities of % 3.0 mS cm at room temperature. Besides this first report of astructurally characterized lithium phosphidoaluminate, another compound of the composition Li 3 AlP 2 was mentioned already in 1952 and described with an orthorhombic distorted CaF 2 -type structure, in which the phosphorus atoms form ad istorted cubic close packing, althoughw ithoutr eliable crystallographic data. [14] Twoy ears later,t he corresponding gallium compound Li 3 GaP 2 was also postulated. [15] Despite the poorly characterized structure model, quantum-chemical calculations of Li 3 AlP 2 and Li 3 GaP 2 were performed, anticipating the model of vertex-sharing AlP 4 tetrahedra. [16][17][18] As forl ithium phosphidotetrelates, lithium phosphidoaluminates can also be connected on al ine in a Gibbs composition triangle (Finetti diagram). Li 3 AlP 2 is located on the line in the phase system Li-Al-P connecting Li 3 Pa nd AlP ( Figure S7, Supporting Information) by reducing Li 9 AlP 4 by two units of Li 3 P( Li 3 AlP 2 = Li 9 AlP 4 À2 Li 3 P). Assuming ac harge balanced valence compound, the degree of connectivity of the AlP 4 tetrahedra in Li 3 AlP 2 mustb eh igher, and isolated tetrahedra as observed in Li 9 AlP 4 cannot occur.Here...

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Section: Resultssupporting

confidence: 81%

Synthesis, Structure, Solid‐State NMR Spectroscopy, and Electronic Structures of the Phosphidotrielates Li₃AlP₂ and Li₃GaP₂

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Raudaschl‐Sieber

et al. 2020

Chemistry A European J

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“…+ 4500 ppm) verschoben, [21] d. h. auch zu tieferem Feld als für kristallines GaP ( 69 Ga: + 307 ppm) beobachtet [22] wurde. Auch hinsichtlich der 31 PVerschiebungen gibt es zwischen 1 und festem GaP ( 31 P: + 146 ppm) [23] keine augenfälligen Parallelen. Offenbar führt die polare Umgebung von vier Ga-Atomen mit je vier PAtomen in festem GaP trotz z. T. ähnlicher Anordnung wie in 1 (z.…”

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[Ga₁₆(PtBu₂)₁₀]: ein mit Galliumphosphid ummantelter Kern aus vier nackten Ga‐Atomen?

2003

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“…[22] There are also no striking parallels between the 31 P chemical shifts of 1 and solid GaP ( 31 P: + 146 ppm). [23] Despite their partially similar structures, the polar environment of four Ga atoms surrounded by four P atoms in solid GaP clearly leads to a significantly different local electronic structure than in 1 (e.g. for P2), with its largely nonpolar PÀC bonds.…”

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confidence: 99%

[Ga₁₆(PtBu₂)₁₀]: A Gallium Phosphide Sheathed Core of Four Naked Ga Atoms?

2003

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31P chemical shifts in BP, GaP and InP

Cited by 12 publications

References 9 publications

Synthesis, Structure, Solid‐State NMR Spectroscopy, and Electronic Structures of the Phosphidotrielates Li₃AlP₂ and Li₃GaP₂

Synthesis, Structure, Solid‐State NMR Spectroscopy, and Electronic Structures of the Phosphidotrielates Li₃AlP₂ and Li₃GaP₂

[Ga₁₆(PtBu₂)₁₀]: ein mit Galliumphosphid ummantelter Kern aus vier nackten Ga‐Atomen?

[Ga₁₆(PtBu₂)₁₀]: A Gallium Phosphide Sheathed Core of Four Naked Ga Atoms?

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31P chemical shifts in BP, GaP and InP

Cited by 12 publications

References 9 publications

Synthesis, Structure, Solid‐State NMR Spectroscopy, and Electronic Structures of the Phosphidotrielates Li3AlP2 and Li3GaP2

Synthesis, Structure, Solid‐State NMR Spectroscopy, and Electronic Structures of the Phosphidotrielates Li3AlP2 and Li3GaP2

[Ga16(PtBu2)10]: ein mit Galliumphosphid ummantelter Kern aus vier nackten Ga‐Atomen?

[Ga16(PtBu2)10]: A Gallium Phosphide Sheathed Core of Four Naked Ga Atoms?

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Synthesis, Structure, Solid‐State NMR Spectroscopy, and Electronic Structures of the Phosphidotrielates Li₃AlP₂ and Li₃GaP₂

Synthesis, Structure, Solid‐State NMR Spectroscopy, and Electronic Structures of the Phosphidotrielates Li₃AlP₂ and Li₃GaP₂

[Ga₁₆(PtBu₂)₁₀]: ein mit Galliumphosphid ummantelter Kern aus vier nackten Ga‐Atomen?

[Ga₁₆(PtBu₂)₁₀]: A Gallium Phosphide Sheathed Core of Four Naked Ga Atoms?