Halbleiter oder eindimensionales Metall und Supraleiter durch Tellur‐π‐Stapelung

Ahmed, Ejaz; Beck, Johannes; Daniels, Jörg; Doert, Thomas; Eck, Steffen; Heerwig, Andreas; Isaeva, Anna; Lidin, Sven; Ruck, Michael; Schnelle, Walter; Stankowski, Alexander

doi:10.1002/ange.201200895

Cited by 23 publications

(9 citation statements)

References 40 publications

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“…The second Br remains at the [Te 4 ] 2+ but jumps between two Te atoms. These findings support the proposed reaction mechanism for the formation of tellurium polycations in Lewis‐acidic media by halide abstraction with subsequent redox reaction or rearrangement , , , ,…”

Section: Discussionsupporting

confidence: 83%

“…Furthermore, utilization of ILs can lead to extraordinary physical properties: Te 4 [Bi 0.67 Cl 4 ] obtained from a classic gas‐phase transport reaction is a semiconductor. However, transition to an IL‐based synthesis yielded the closely related compound Te 4 [Bi 0.74 Cl 4 ], which proved to be a one‐dimensional metal and type‐I superconductor , . In particular, three different ternary compounds (and polycations) can be synthesized in the Lewis‐acidic IL [C 4 C 1 Im]Cl · n AlCl 3 ( n = 1.3–1.5): the already mentioned Te 4 [Bi 0.74 Cl 4 ], as well as the closely related semiconductors Te 4 [Bi 6 Cl 20 ] and Te 8 [Bi 4 Cl 14 ] .…”

Section: Introductionmentioning

confidence: 99%

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Theoretical Investigation of the Te₄Br₂ Molecule in Ionic Liquids

Elfgen

Hollóczki

Ray

et al. 2016

Zeitschrift anorg allge chemie

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Material synthesis in ionic liquids, at or near room temperature, is currently a subject of immense academic interest. In order to illuminate molecular‐level details and the underlying chemistry, we carried out molecular simulations of a single Te4Br2 molecule dissolved in the ionic liquid 1‐ethyl‐3‐methylimidazolium chloride, as well as in the ionic liquid mixed with aluminum chloride. Although the ethyl side chain is much too short to show detailed microheterogeneity, significant structuring with the small chloride anions is seen in case of the pure ionic liquid. In the case of the mixture, formation of larger anionic clusters is distinctly observed and analyzed. Due to the tendency of ionic liquids to dissociate, there is a pronounced shift to elongated Te–Br distances in both investigated solvents. However, only in the AlCl3‐containing liquid, we observe the reaction of the open chain‐like Te4Br2 molecule to a closed square‐like Te4Br+ and AlCl3Br– ion. The molecular arrangement of the [Te4]2+ unit shows negligible deviation from that in the experimental crystal structure.

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Section: Discussionsupporting

confidence: 83%

Section: Introductionmentioning

confidence: 99%

Theoretical Investigation of the Te₄Br₂ Molecule in Ionic Liquids

Elfgen

Hollóczki

Ray

et al. 2016

Zeitschrift anorg allge chemie

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“…Sie ist nach wenigen Stunden abgeschlossen. Die bemerkenswerte elektrische Leitfähigkeit der Phase erreichen alternative Herstellungsmethoden über chemischen Gasphasentransport nicht 4…”

Section: Solvens Benötigtunclassified

Sanfte Festkörperchemie

et al. 2013

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“…Kanatzidis et al,13 Feldmann et al,14 Ruck et al,15 and Huang et al16 have successfully applied the chemistry of ionic liquids to the synthesis and isolation of several new polycations. Among them are the discrete heteropolycations [Sb 7 S 8 Br 2 ] 3+ ,13a [Cr 7 S 8 Cl 2 (NH 3 ) 14.5 (H 2 O) 1.5 ] 3+ ,16 [Bi 3 GaS 5 ] 2+ ,14 and [Sb 10 Se 10 ] 2+ ,15a the two‐dimensional networks [Bi 2 Te 2 Br] + ,13b [Sb 2 Te 2 Br] + ,13b and [Bi 2 Se 2 Br] + ,13c and the three‐dimensional polycationic chalcogenide–aluminum–halide framework of [(Bi 4 Te 4 Br 2 )(Al 2 X 6 )] 2+ (X = Cl, Br),13c and, moreover, a one‐dimensional metal Te 4 [Bi 0.74 Cl 4 ] synthesized in ionic liquid shows interesting superconducting properties 15b…”

Section: Introductionmentioning

confidence: 99%

[Sb₇Se₈Br₂]³⁺and [Sb₁₃Se₁₆Br₂]⁵⁺– Double and Quadruple Spiro Cubanes from Ionic Liquids

et al. 2014

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The reaction of antimony and selenium in the bromine‐rich Lewis acidic ionic liquid [BMIm]Br·4.7AlBr3 (BMIm: 1‐butyl‐3‐methylimidazolium) in the presence of a small amount of NbCl5 at 160 °C yielded dark‐red crystals of [Sb7Se8Br2][AlX4]3. For X = Cl0.15(1)Br0.85(1), the compound is isostructural to [Sb7S8Br2][AlCl4]3 [P212121, a = 12.5132(5) Å, b = 17.7394(6) Å, c = 18.3013(6) Å]. For a higher chlorine content, X = Cl0.58(1)Br0.42(1), a slightly disordered variant with a bisected unit cell is found [P21212, a = 12.3757(3) Å, b = 17.4116(5) Å, c = 9.0420(2) Å]. The [Sb7Se8Br2]3+ heteropolycation (C2 symmetry) is a spiro double‐cubane with an antimony atom on the shared corner. From this distorted octahedrally coordinated central atom, tricoordinate selenium and antimony atoms alternate in the bonding sequence. The terminal antimony atoms each bind to a bromine atom. Quantum chemical calculations confirm polar covalent Sb–Se bonding within the cubes and indicate three‐center, four‐electron bonds for the six‐coordinate spiro atoms. The calculated charge distribution reflects the electron‐donor role of the antimony atoms. The use of a chlorine‐rich ionic liquid resulted in the formation of triclinic [Sb13Se16Br2][AlX4]5 with X = Cl0.80(1)Br0.20(1) [P$\bar {1}$, a = 9.0842(5) Å, b = 19.607(1) Å, c = 21.511(1) Å, α = 64.116(6)°, β = 79.768(7)°, γ = 88.499(7)°]. The cationic cluster [Sb13Se16Br2]5+ is a bromine‐terminated spiro quadruple‐cubane. This 31 atom concatenation of four cubes is assumed to be the largest known discrete main group polycation. A similar reaction in a chloride‐free system yielded [Sb7Se8Br2][Sb13Se16Br2][AlBr4]8. In its monoclinic structure [P2/c, a = 27.214(5) Å, b = 9.383(2) Å, c = 22.917(4) Å, β = 101.68(1)°], the two types of polycations alternate in layers along the a axis. In the series [Sb4+3nSe4+4nBr2](2+n)+, these cations are the members with n = 1 and 3.

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Halbleiter oder eindimensionales Metall und Supraleiter durch Tellur‐π‐Stapelung

Cited by 23 publications

References 40 publications

Theoretical Investigation of the Te₄Br₂ Molecule in Ionic Liquids

Theoretical Investigation of the Te₄Br₂ Molecule in Ionic Liquids

Sanfte Festkörperchemie

[Sb₇Se₈Br₂]³⁺and [Sb₁₃Se₁₆Br₂]⁵⁺– Double and Quadruple Spiro Cubanes from Ionic Liquids

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Halbleiter oder eindimensionales Metall und Supraleiter durch Tellur‐π‐Stapelung

Cited by 23 publications

References 40 publications

Theoretical Investigation of the Te4Br2 Molecule in Ionic Liquids

Theoretical Investigation of the Te4Br2 Molecule in Ionic Liquids

Sanfte Festkörperchemie

[Sb7Se8Br2]3+and [Sb13Se16Br2]5+– Double and Quadruple Spiro Cubanes from Ionic Liquids

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Theoretical Investigation of the Te₄Br₂ Molecule in Ionic Liquids

Theoretical Investigation of the Te₄Br₂ Molecule in Ionic Liquids

[Sb₇Se₈Br₂]³⁺and [Sb₁₃Se₁₆Br₂]⁵⁺– Double and Quadruple Spiro Cubanes from Ionic Liquids