A Borosilicide with Clathrate VIII Structure

Hübner, Julia‐Maria; Carrillo‐Cabrera, W.; Koželj, Primož; Prots, Yurii; Baitinger, Michael; Schwarz, Ulrich; Jung, Walter

doi:10.1021/jacs.2c04745

Cited by 3 publications

(2 citation statements)

References 27 publications

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“…Based on previous experience with structure solution from electron diffraction or PEDT data, − we tested the method on the product of an unusual topochemical reaction. This continues our investigations on the synthesis of new compounds by heterogeneous reactions including mass transport and structural transformations in the solid state. − The compounds obtained in this way are often, but not necessarily, metastable and cannot be produced by other methods.…”

Section: Introductionmentioning

confidence: 99%

Electron Diffraction Tomography on Two-Phase Nanolamellae of Topochemically Synthesized Cu(Sb₂S₃)Cl

Carrillo-Cabrera,

Dreimann,

Grasser

et al. 2024

Inorg. Chem.

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The dark red semiconductor Cu(Sb 2 S 3 )Cl was obtained by leaching the layered precursor Cu(Sb 2 S 3 )[AlCl 4 ] in a 0.1 M aqueous HCl solution. The selective extraction of AlCl 3 yielded a mica-like lamellar product of poor crystallinity. Misalignment of lamellae down to the nanoscale prevented structure determination by conventional single-crystal X-ray diffraction, but a combination of transmission electron microscopy, selected area electron diffraction, and selected area electron precession diffraction tomography on a nanoscale spot with largely ordered crystalline lamellae revealed the crystal structures of two intergrown modifications. Orthorhombic o-Cu(Sb 2 S 3 )Cl and monoclinic m-Cu(Sb 2 S 3 )Cl have similar layers to the precursor and differ only in the stacking of the layers. These consist of uncharged Sb 2 S 3 strands, whose sulfide ions, together with chloride ions, coordinate the copper(I) cations. Only one chloride ion remained from the [AlCl 4 ] − group. DFT calculations confirm the structure solution for the orthorhombic form and suggest that the monoclinic structure is metastable against transformation to o-Cu(Sb 2 S 3 )Cl.

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Section: Introductionmentioning

confidence: 99%

Electron Diffraction Tomography on Two-Phase Nanolamellae of Topochemically Synthesized Cu(Sb₂S₃)Cl

Carrillo-Cabrera,

Dreimann,

Grasser

et al. 2024

Inorg. Chem.

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“…Under compression, a volume reduction and, therefore, a densification of matter occurs, resulting in increased electrostatic interactions . For the case of group-14 elements, a wide range of novel guest–host framework types and compositions have been synthesized under high-pressure conditions, in addition to the clathrate structures that are formed at low pressure. − Many framework types exhibit variable guest atom occupancies, and thus tunable electronic structures, and in some cases, guest atoms or intercalants may be topotactically removed to produce novel tetrel allotropes. − The exploration of higher-order systems with the possibility of multipartite frameworks adds additional degrees of freedom to expand the structural diversity of 3D frameworks.…”

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confidence: 99%

A Sodium Germanosilicide with Unusual Network Topology

Hübner,

Shiell,

Guńka

et al. 2024

J. Am. Chem. Soc.

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The germanosilicide Na 4−x Ge y Si 16−y (0.4 ≤ x ≤ 1.1, 4.7 ≤ y ≤ 9.3) was synthesized under high-pressure, hightemperature conditions. The novel guest−host compound comprises a unique tetrel framework with dual channels housing sodium and smaller, empty (Si,Ge) 9 units. The arrangement represents a new structure type with an overall structural topology that is closely related to a hypothetical carbon allotrope. Topological analysis of the structure revealed that the guest environment space cannot be tiled with singular polyhedra as in cage compounds (e.g., clathrates). The analysis of natural tilings provides a convenient method to unambiguously compare related tetrel-rich structures and can help elucidate new possible structural arrangements of intermetallic compounds.

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Na₂B₆Si₂: A Prototype Silico-boride with Closo (B₆)^2– Clusters

Carrillo-Cabrera,

Hübner,

Freccero

et al. 2024

J. Am. Chem. Soc.

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The compound Na2B6Si2 was synthesized under high-pressure, high-temperature conditions at pressures ranging from 6 to 9.5 GPa and temperatures from 1070 to 1270 K before quenching to room temperature followed by slow decompression. The crystal structure was determined from microcrystals using precession-assisted electron diffraction tomography, validated by dynamical refinement and full-profile refinements using optimized coordinates from quantum chemical calculations (space group R3̅m, Pearson symbol hR30, a = 5.0735(1) Å and c = 16.0004(7) Å). The atomic arrangement consists of a unique framework formed by electron-precise octahedral closo (B6)2– clusters connected via ethane-like (Si2)0 dumbbells. The Na+ cations occupy cavities in the hierarchical variation of a Heusler-type framework. The balance (Na+)2([B6]2–)(Si0)2 reveals an electron precise Zintl-Wade phase, which is in line with electronic band structure calculations predicting semiconducting behavior.

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A Borosilicide with Clathrate VIII Structure

Abstract: The high-pressure phase Na 8 B x Si 46– x (3 < x < 5) is the first representative of a borosilicide crystallizing in the rarely occurring clathrate VIII type structure. Crystals with composition Na 8 B 4 Si 42 (space group I 43̅ m ; a = 9.7187(2) Å; Pearson symbol … Show more

Cited by 3 publications

References 27 publications

Electron Diffraction Tomography on Two-Phase Nanolamellae of Topochemically Synthesized Cu(Sb₂S₃)Cl

Electron Diffraction Tomography on Two-Phase Nanolamellae of Topochemically Synthesized Cu(Sb₂S₃)Cl

A Sodium Germanosilicide with Unusual Network Topology

Na₂B₆Si₂: A Prototype Silico-boride with Closo (B₆)^2– Clusters

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A Borosilicide with Clathrate VIII Structure

Abstract: The high-pressure phase Na 8 B x Si 46– x (3 < x < 5) is the first representative of a borosilicide crystallizing in the rarely occurring clathrate VIII type structure. Crystals with composition Na 8 B 4 Si 42 (space group I 43̅ m ; a = 9.7187(2) Å; Pearson symbol … Show more

Cited by 3 publications

References 27 publications

Electron Diffraction Tomography on Two-Phase Nanolamellae of Topochemically Synthesized Cu(Sb2S3)Cl

Electron Diffraction Tomography on Two-Phase Nanolamellae of Topochemically Synthesized Cu(Sb2S3)Cl

A Sodium Germanosilicide with Unusual Network Topology

Na2B6Si2: A Prototype Silico-boride with Closo (B6)2– Clusters

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Product

Resources

About

Electron Diffraction Tomography on Two-Phase Nanolamellae of Topochemically Synthesized Cu(Sb₂S₃)Cl

Electron Diffraction Tomography on Two-Phase Nanolamellae of Topochemically Synthesized Cu(Sb₂S₃)Cl

Na₂B₆Si₂: A Prototype Silico-boride with Closo (B₆)^2– Clusters