Determination of stoichiometry and site disorder in the complex intermetallics

Wu, Dongmei; Huang, Mianliang; Lograsso, Thomas A.; McCallum, R. W.; Mozharivski, Y.; Llobet, Anna

doi:10.1016/j.jallcom.2006.09.075

“…Single‐stranded substructures were observed in other intermetallic solids, for instance in Pr 6 Ni 1.76 Si 3 , [24a] Pr 5 Ni 1.9 Si 3 , [24b] Ce 6 Ni 2 Si 3 , [25] Nd 6 Co 1.67 Si 3 , [26] Pr 6 Co 1.67 Si 3 , [27] K 10 Ga 3 Sb 6.33 , [28] K 10 Ga 3 As 6.33 , [28] and K 10 Ga 3 Bi 6.65 , [29] some of which were also interpreted as line‐up of disordered dumbbells.…”

Section: Resultsmentioning

confidence: 97%

Between Elemental Match and Mismatch: From K₁₂Ge_3.5Sb₆ to Salts of (Ge₂Sb₂)²⁻, (Ge₄Sb₁₂)⁴⁻, and (Ge₄Sb₁₄)⁴⁻

Beuthert

¹

,

Pan

²

,

Guggolz

³

et al. 2022

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The solid mixture "K 2 GeSb" was shown to comprise single-crystalline K 12 Ge 3.5 Sb 6 (1), a double salt of K 5 [GeSb 3 ] with carbonate-like [GeSb 3 ] 5À anions, and the metallic Zintl phase K 2 Ge 1.5 . Extraction of 1 with ethane-1,2-diamine in the presence of crypt-222 afforded [K(crypt-222)] + salts of several novel binary Zintl anions: (Ge 2 Sb 2 ) 2À (in 2), (Ge 4 Sb 12 ) 4À (in 3), and in the presence of [AuMePPh 3 ] also (Ge 4 Sb 14 ) 4À (in 4). The anion in 2 represents a predicted, yet heretofore missing pseudo-tetrahedral anion. 4 comprises a cluster analogous to (Ge 4 Bi 14 ) 4À and (Ga 2 Bi 16 ) 4À , and thus one of the most Sb-rich binary p-block anions. The unprecedented cluster topology in 3 can be viewed as a defect-version of the one in 4 upon following a "dead end" of cluster growth. The findings indicate that Ge and Sb atoms are at the border of a well-matching and a mismatch elemental combination. We discuss the syntheses, the geometric structures, and the electronic structures of the new compounds.

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Between Elemental Match and Mismatch: From K₁₂Ge_3.5Sb₆ to Salts of (Ge₂Sb₂)²⁻, (Ge₄Sb₁₂)⁴⁻, and (Ge₄Sb₁₄)⁴⁻

Beuthert

¹

,

Pan

²

,

Guggolz

³

et al. 2022

View full text Add to dashboard Cite

The solid mixture "K 2 GeSb" was shown to comprise single-crystalline K 12 Ge 3.5 Sb 6 (1), a double salt of K 5 [GeSb 3 ] with carbonate-like [GeSb 3 ] 5À anions, and the metallic Zintl phase K 2 Ge 1.5 . Extraction of 1 with ethane-1,2-diamine in the presence of crypt-222 afforded [K(crypt-222)] + salts of several novel binary Zintl anions: (Ge 2 Sb 2 ) 2À (in 2), (Ge 4 Sb 12 ) 4À (in 3), and in the presence of [AuMePPh 3 ] also (Ge 4 Sb 14 ) 4À (in 4). The anion in 2 represents a predicted, yet heretofore missing pseudo-tetrahedral anion. 4 comprises a cluster analogous to (Ge 4 Bi 14 ) 4À and (Ga 2 Bi 16 ) 4À , and thus one of the most Sb-rich binary p-block anions. The unprecedented cluster topology in 3 can be viewed as a defect-version of the one in 4 upon following a "dead end" of cluster growth. The findings indicate that Ge and Sb atoms are at the border of a well-matching and a mismatch elemental combination. We discuss the syntheses, the geometric structures, and the electronic structures of the new compounds.

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La_n(n+1)+xNi_n(n+5)+ySi_{(n+1)(n+2)–z}: A Symmetric Mirror Homologous Series in the La–Ni–Si System

Grilli,

Smetana,

Ahmed

et al. 2023

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A series of four homologous silicides have been discovered during systematic explorations in the central part of the La–Ni–Si system at 1000 °C. All compounds La12.5Ni28.0Si18.3 (n = 3; a = 28.8686(8), c = 4.0737(2) Å, Z = 3), La22.1Ni39.0Si27.8 (n = 4; a = 20.9340(6), c = 4.1245(2) Å, Z = 1), La32.9Ni49.8Si39.3 (n = 5; a = 24.946(1), c = 4.1471(5) Å, Z = 1), and La44.8Ni66.1Si53.4 (n = 6; a = 28.995(5), c = 4.158(1) Å, Z = 1) crystallize in the hexagonal space group P63/m and can be generalized according to La n(n+1)+x Ni n(n+5)+y Si(n+1)(n+2)–z with n = 3–6. Their crystal structures are based on AlB2-type building blocks, fused La-centered Ni6Si6 hexagonal prisms, yielding larger oligomeric equilateral domains with the edge size equal to n. The domains extend along the c axis and show checkered ordering of the cationic and anionic parts, while all their atoms are located on mirror planes. La n(n+1)+x Ni n(n+5)+y Si(n+1)(n+2)–z can be considered as a mirror series to the La-rich La(n+1)(n+2)Ni n(n–1)+2Si n(n+1), where an exchange of the formal cationic and anionic sites, i.e., La and Si, occurs. The La–Ni–Si system is the first system where two such analogous series have been observed.

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Determination of stoichiometry and site disorder in the complex intermetallics

Cited by 5 publications

References 9 publications

Between Elemental Match and Mismatch: From K₁₂Ge_3.5Sb₆ to Salts of (Ge₂Sb₂)²⁻, (Ge₄Sb₁₂)⁴⁻, and (Ge₄Sb₁₄)⁴⁻

Between Elemental Match and Mismatch: From K₁₂Ge_3.5Sb₆ to Salts of (Ge₂Sb₂)²⁻, (Ge₄Sb₁₂)⁴⁻, and (Ge₄Sb₁₄)⁴⁻

Between Elemental Match and Mismatch: From K₁₂Ge_3.5Sb₆ to Salts of (Ge₂Sb₂)²⁻, (Ge₄Sb₁₂)⁴⁻, and (Ge₄Sb₁₄)⁴⁻

La_n(n+1)+xNi_n(n+5)+ySi_{(n+1)(n+2)–z}: A Symmetric Mirror Homologous Series in the La–Ni–Si System

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Determination of stoichiometry and site disorder in the complex intermetallics

Cited by 5 publications

References 9 publications

Between Elemental Match and Mismatch: From K12Ge3.5Sb6 to Salts of (Ge2Sb2)2−, (Ge4Sb12)4−, and (Ge4Sb14)4−

Between Elemental Match and Mismatch: From K12Ge3.5Sb6 to Salts of (Ge2Sb2)2−, (Ge4Sb12)4−, and (Ge4Sb14)4−

Between Elemental Match and Mismatch: From K12Ge3.5Sb6 to Salts of (Ge2Sb2)2−, (Ge4Sb12)4−, and (Ge4Sb14)4−

Lan(n+1)+xNin(n+5)+ySi(n+1)(n+2)–z: A Symmetric Mirror Homologous Series in the La–Ni–Si System

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Between Elemental Match and Mismatch: From K₁₂Ge_3.5Sb₆ to Salts of (Ge₂Sb₂)²⁻, (Ge₄Sb₁₂)⁴⁻, and (Ge₄Sb₁₄)⁴⁻

Between Elemental Match and Mismatch: From K₁₂Ge_3.5Sb₆ to Salts of (Ge₂Sb₂)²⁻, (Ge₄Sb₁₂)⁴⁻, and (Ge₄Sb₁₄)⁴⁻

Between Elemental Match and Mismatch: From K₁₂Ge_3.5Sb₆ to Salts of (Ge₂Sb₂)²⁻, (Ge₄Sb₁₂)⁴⁻, and (Ge₄Sb₁₄)⁴⁻

La_n(n+1)+xNi_n(n+5)+ySi_{(n+1)(n+2)–z}: A Symmetric Mirror Homologous Series in the La–Ni–Si System