Polyanionische Cluster und Netzwerke der frühen p-Metalle im Festkörper: jenseits der Zintl-Grenze

Corbett, John D.

doi:10.1002/(sici)1521-3757(20000218)112:4<682::aid-ange682>3.0.co;2-3

Cited by 115 publications

(9 citation statements)

References 135 publications

(90 reference statements)

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“…A number of compounds featuring novel and interesting structural properties have been obtained from these combinations of elements; however, no evidence for the existence of “isolated” thallium(−I) was gained. Instead, in each case thallium cluster ions were identified, corroborating the well-known propensity of thallium in negative oxidation states to form homoatomic clusters. , Here we report on Cs 18 Tl 8 O 6 (Figure a) containing a homocubane-like clusteranion with the shape of a double tetrahedron ( stella quadrangula or tetrahedral star), not found before in compounds containing covalently bonded homoatomic clusters. An isoelectronic clusteranion was detected previously in Cs 8 Tl 8 O, however, with the different shape of a parallelepiped.…”

Section: Introductionsupporting

confidence: 88%

Homoatomic Stella Quadrangula [Tl₈]⁶⁻in Cs₁₈Tl₈O₆, Interplay of Spin−Orbit Coupling, and Jahn−Teller Distortion

et al. 2010

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Cs(18)Tl(8)O(6) was synthesized reacting the binary compounds CsTl and Cs(2)O. According to single crystal X-ray analysis, the title compound crystallizes as a novel structure type in the cubic space group I23 and is diamagnetic. The electronic structure of the extended solid and of excised Cs(6)Tl(8) clusters has been examined by relativistic density functional calculations including spin-orbit coupling. Cs(18)Tl(8)O(6) comprises a clusteranion [Tl(8)](6-) in the shape of a tetrahedral star. An isoelectronic cluster was found previously in Cs(8)Tl(8)O, however, with the shape of a parallelepiped. Both clusteranions can be derived from a homocubane unit by displacive distortions. It has been shown by quantum mechanical analyses that the closed-shell electronic structure of the parallelepiped is the result of a Jahn-Teller distortion, while in contrast the tetrahedral star in Cs(18)Tl(8)O(6) would still exhibit an open-shell degenerate HOMO within a scalar relativistic approximation. Only if spin-orbit coupling is considered, a closed-shell electronic system is obtained in accordance with the diamagnetic behavior of Cs(18)Tl(8)O(6).

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Section: Introductionsupporting

confidence: 88%

Homoatomic Stella Quadrangula [Tl₈]⁶⁻in Cs₁₈Tl₈O₆, Interplay of Spin−Orbit Coupling, and Jahn−Teller Distortion

et al. 2010

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“…All of the ligand-free anionic intermetalloid clusters mentioned above were characterized in salts obtained from reactions of p block element Zintl anions with organometallic d or f block metal compounds . A number of discrete intermetalloid cage clusters with single endohedral d block metal atoms also appear in polar intermetallic phases with group 13 elements (neat solid-state compounds), including [Zn@E 10 ] 8– in K 8 ZnE 10 (E = In, Tl), [Ni@Ga 10 ] 10– in Na 10 NiGa 10 , [M@E 10 ] 10– in K 10 ME 10 (M = Ni, Pd, Pt; E = In, Tl), [Pd@Tl 11 ] 8– in A 8 PdTl 11 (A = K, Rb, Cs), and [M@Tl 12 ] 12– in Na 14 K 6 Tl 18 M (M = Zn, Cd, Hg) . Also, cationic cage clusters with interstitial atoms are known in case of Bi, [Pd@Bi 10 ] 4+ , for example in Bi 14 PdBr 16 , and [Au@Bi 10 ] 5+ in AuBi 14−δ Sn 2+δ X 21−δ (δ ≈ 0.4) with X = Cl, Br.…”

Section: Introductionmentioning

confidence: 99%

A Bronze Matryoshka: The Discrete Intermetalloid Cluster [Sn@Cu₁₂@Sn₂₀]^12– in the Ternary Phases A₁₂Cu₁₂Sn₂₁ (A = Na, K)

2011

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The synthesis and crystal structure of the first ternary A-Cu-Sn intermetallic phases for the heavier alkali metals A = Na to Cs is reported. The title compounds A(12)Cu(12)Sn(21) show discrete 33-atom intermetalloid Cu-Sn clusters {Sn@Cu(12)@Sn(20)}, which are composed of {Sn(20)} pentagonal dodecahedra surrounding {Cu(12)} icosahedra with single Sn atoms at the center. Na(12)Cu(12)Sn(21) and K(12)Cu(12)Sn(21) were characterized by single-crystal XRD studies, and the successful synthesis of analogous A-Cu-Sn compounds with A = Rb and Cs is deduced from powder XRD data. The isotypic A(12)Cu(12)Sn(21) phases crystallize in the cubic space group Pn ̅3m (No. 224), with the Cu-Sn clusters adopting a face centered cubic arrangement. A formal charge of 12- can be assigned to the {Sn@Cu(12)@Sn(20)} cluster unit, and the interpretation of the title compounds as salt-like intermetallic phases featuring discrete anionic intermetalloid [Sn@Cu(12)@Sn(20)](12-) clusters separated by alkali metal cations is supported by electronic structure calculations. For both Na(12)Cu(12)Sn(21) and K(12)Cu(12)Sn(21), DFT band structure calculations (TB-LMTO-ASA) reveal a band gap. The discrete [Sn@Cu(12)@Sn(20)](12-) cluster is analyzed in consideration of the molecular orbitals obtained from hybrid DFT calculations (Gaussian 09) for the cluster anion. The [Sn@Cu(12)@Sn(20)](12-) cluster MOs can be classified with labels indicating the numbers of radial and angular nodes, in the style of spherical shell models of cluster bonding.

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“…Others (e.g., [Ge 4 –Na–Ge 4 ] 7– in A 7 NaGe 8 with A = K, Rb) show packing schemes very different from those of their binary analogues. These examples along with extensive studies on mixed cation trielides performed by Dong and Corbett , demonstrated that mixing cations of different sizes can be a very useful tool for achieving this balance . Ab initio calculations on the structural differences in NaTl and KTl as well as Li 2 AuBi and Na 2 AuBi support the frequently observed structure-directing effect of cations in Zintl compounds.…”

Section: Introductionmentioning

confidence: 74%

“…For both tetrahedron types, Li atoms cap trigonal faces or bridge edges or coordinate exo at vertices. These coordination modes commonly occur in Zintl cluster sheathing …”

Section: Resultsmentioning

confidence: 99%

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Li₁₈Na₂Ge₁₇—A Compound Demonstrating Cation Effects on Cluster Shapes and Crystal Packing in Ternary Zintl Phases

2014

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The novel ternary Zintl phase Li18Na2Ge17 was synthesized from a stoichiometric melt and characterized crystallographically. It crystallizes in the trigonal space group P31m (No. 157) with a = 17.0905(4) Å, c = 8.0783(2) Å, and V = 2043.43(8) Å(3) (final R indices R1 = 0.0212 and wR2 = 0.0420 for all data). The structure contains three different Zintl anions in a 1:1:1 ratio: isolated anions Ge(4-), tetrahedra [Ge4](4-), and truncated, Li-centered tetrahedra [Li@Ge12](11-), whose hexagonal faces are capped by four Li cations, resulting in the Friauf polyhedra [Li@Li4Ge12](7-). According to the Zintl-Klemm concept, Li18Na2Ge17 is an electronically balanced Zintl phase, as experimentally verified by its diamagnetism. The compound is structurally related to Li7RbGe8, which also contains [Ge4](4-) and [Li@Li4Ge12](7-) in its anionic substructure. However, exchanging the heavier alkali metal cation Rb for Na in the mixed-cation germanides leads to drastic changes in stoichiometry and crystal packing, demonstrating the great effects that cations exert on such Zintl phases through optimized cluster sheathing and space filling.

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Polyanionische Cluster und Netzwerke der frühen p-Metalle im Festkörper: jenseits der Zintl-Grenze

Cited by 115 publications

References 135 publications

Homoatomic Stella Quadrangula [Tl₈]⁶⁻in Cs₁₈Tl₈O₆, Interplay of Spin−Orbit Coupling, and Jahn−Teller Distortion

Homoatomic Stella Quadrangula [Tl₈]⁶⁻in Cs₁₈Tl₈O₆, Interplay of Spin−Orbit Coupling, and Jahn−Teller Distortion

A Bronze Matryoshka: The Discrete Intermetalloid Cluster [Sn@Cu₁₂@Sn₂₀]^12– in the Ternary Phases A₁₂Cu₁₂Sn₂₁ (A = Na, K)

Li₁₈Na₂Ge₁₇—A Compound Demonstrating Cation Effects on Cluster Shapes and Crystal Packing in Ternary Zintl Phases

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Polyanionische Cluster und Netzwerke der frühen p-Metalle im Festkörper: jenseits der Zintl-Grenze

Cited by 115 publications

References 135 publications

Homoatomic Stella Quadrangula [Tl8]6−in Cs18Tl8O6, Interplay of Spin−Orbit Coupling, and Jahn−Teller Distortion

Homoatomic Stella Quadrangula [Tl8]6−in Cs18Tl8O6, Interplay of Spin−Orbit Coupling, and Jahn−Teller Distortion

A Bronze Matryoshka: The Discrete Intermetalloid Cluster [Sn@Cu12@Sn20]12– in the Ternary Phases A12Cu12Sn21 (A = Na, K)

Li18Na2Ge17—A Compound Demonstrating Cation Effects on Cluster Shapes and Crystal Packing in Ternary Zintl Phases

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Homoatomic Stella Quadrangula [Tl₈]⁶⁻in Cs₁₈Tl₈O₆, Interplay of Spin−Orbit Coupling, and Jahn−Teller Distortion

Homoatomic Stella Quadrangula [Tl₈]⁶⁻in Cs₁₈Tl₈O₆, Interplay of Spin−Orbit Coupling, and Jahn−Teller Distortion

A Bronze Matryoshka: The Discrete Intermetalloid Cluster [Sn@Cu₁₂@Sn₂₀]^12– in the Ternary Phases A₁₂Cu₁₂Sn₂₁ (A = Na, K)

Li₁₈Na₂Ge₁₇—A Compound Demonstrating Cation Effects on Cluster Shapes and Crystal Packing in Ternary Zintl Phases