Na30.5AgxGa60—x: A Three-Dimensional Network Composed of Ga3, Ga12, and Ga18 Clusters

Henning, Robert; Corbett, John D.

doi:10.1002/1521-3749(200212)628:12<2715::aid-zaac2715>3.0.co;2-a

Cited by 8 publications

(13 citation statements)

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“…These may be generated in different ways, such as by the formation of vacancies at specific cluster sites or through substitution of even modest amounts of electron-poorer elements in the clusters. For example, the tubular clusters, (In/Cd) 18 and (Ga/Ag) 18 , have been found in Na 8 K 23 Cd 12 In 48 3 and Na 30 (Ga 56 Ag 4 ), respectively, and different kinds of M 60 (M = Al/Zn or Tl/Cd) buckyballs occur in Mg 2 - y (Zn x Al 1 - x ) 3+ y and Na 13 (Cd ∼ 0.70 Tl ∼ 0.30 ) 27 with Bergman-type structures.…”

Section: Introductionmentioning

confidence: 99%

Electronic Stabilization Effects: Three New K−In−T (T = Mg, Au, Zn) Network Compounds

Corbett

2006

Inorg. Chem.

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The ternary compounds K(34)In(91.05(9))Mg(13.95(9)) (I), K(34)In(96.19(6))Au(8.81(6)) (II), and K(34)In(89.95(1))Zn(13.05(7)) (III) have been synthesized by high-temperature means and structurally characterized by single-crystal X-ray diffraction methods. All are analogues of earlier products in which Li is substituted for some In in a hypothetical K(34)In(105) lattice. They consist of complex three-dimensional anionic networks built of In(12) icosahedra and M(28) triply fused icosahedra (M = In or In/T and T = Mg, Au, or Zn). The K atoms bridge between cluster faces or edges and form K(136) clathrate-IotaIota type networks. Two neighboring M(28) units are interconnected by an M atom to form a sandwich complex (M(28))M(M(28)) in I and II or by a Zn-Zn dimer in (M(28))ZnZn(M(28)) in III. Mixed In/T sites only occur in the M(28) portions. Phase stabilization through electronic tuning is present in all three via substitution of the electron-poorer T elements for In. Extended Hückel analyses indicate that all metal-metal bonding within the M(28) cluster appears to be optimized in I and III even though both are metallic. The size of the substituted element is also important in the structural features, as is especially shown by the Zn compound.

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Section: Introductionmentioning

confidence: 99%

Electronic Stabilization Effects: Three New K−In−T (T = Mg, Au, Zn) Network Compounds

Corbett

2006

Inorg. Chem.

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“…The structures of 1 and 2 are very similar, except that (1) the Ca5 site has very diffuse electron density in 1, but the corresponding atom in 2 splits into two separated parts (see Figure 1) and (2) the Wyckoff 1a (0, 0, 0) site, which is the center of a M 18 tubular cluster, is empty in 1, and it is occupied by Ca6 with a refined occupancy of 45.7(6)% in 2. Split sites were also found for some other related structures containing tunnels, e.g., Na 30.5 Ag 2.6 Ga 57.4 , 39 but, in general, the total number of atoms in tunnels is less than 3 per formula. The exception is Ca 24.7 Yb 6.7 Ni 9 Zn 54 , 46 in which, however, the 3.4 Ca atoms in the tunnel (cf.…”

Section: ■ Results and Discussionmentioning

confidence: 76%

“…This percentage is about 2.4 times the contribution of Na−Ga bonds in "Na 30 Ga 60 ", a model built from the structure of isostructural Na 30.5 Ag 6.4 Ga 53.6 . 39 Apparently, the difference between the formal negative charge of the zinc network and the formal positive charge from calcium can be smeared out by the pronounced covalent interactions. In other words, the present phase may be referred to as a Zintl-like polar phase with an open-shell electronic structure.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Lithiation-Induced Zinc Clustering of Zn₃, Zn₁₂, and Zn₁₈ Units in Zintl-Like Ca_∼30Li_3+xZn_60–x (x = 0.44–1.38)

Lin

2014

Inorg. Chem.

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Zinc clusters are not common for binary intermetallics with relatively low zinc content, but this work shows that zinc clustering can be triggered by lithiation, as exemplified by Ca(∼30)Li(3+x)Zn(60-x), P6/mmm, Z = 1, which can be directly converted from CaZn(2). Two end members of the solid solution (x = 0.44 and 1.38) were established and structurally characterized by single-crystal X-ray diffraction analyses: Ca(30)Li(3.44(6))Zn(59.56(6)), a = 15.4651(9) Å, c = 9.3898(3) Å; Ca(30.45(2))Li(4.38(6))Zn(58.62(6)), a = 15.524(3) Å, c = 9.413(2) Å. The structures of Ca(∼30)Li(3+x)Zn(60-x) feature a condensed anionic network of Zn(3) triangles, lithium-centered Zn(12) icosahedra, and arachno-(Zn,Li)18 tubular clusters that are surrounded respectively by Ca(14), Ca(20), and Ca(30) polyhedra. These polyhedra share faces and form a clathrate-like cationic framework. The specific occupation of lithium in the structure is consistent with theoretical "coloring" analyses. Analysis by the linear muffin-tin orbital (LMTO) method within the atomic sphere approximation reveals that Ca(∼30)Li(3+x)Zn(60-x) is a metallic, Zintl-like phase with an open-shell electronic structure. The contribution of Ca-Zn polar covalent interactions is about 41%.

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“…4 Ga 53.6 revealed Ga 3 triangles, Ga 12 icosahedra, and Ga 18 hexacapped hexagonal prism structures all interconnected into a threedimensional network. 79 Zig-zag chains of gallium atoms were observed in a series of lanthanum gallium tin antimonides. 80 A novel "oxidation" of RbGa 3 occurred through the substitution of gold for gallium, and this structure had layers of interlinked gallium dodecahedral clusters.…”

Section: Galliummentioning

confidence: 99%

4 Aluminium, gallium, indium, and thallium

Maher

2003

Annu. Rep. Prog. Chem., Sect. A: Inorg. Chem.

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The chemistry of metalloid cluster compounds for Al, Ga and In dominate current Group 13 chemistry; a review by Schnepf and Schnöckel summarizes the situation for Al and Ga. 13b The first direct observation of radicals by EPR in the activation of a Zeigler-Natta system is both interesting and important for our understanding of these catalysts. 50b For gallium and indium chemistry, a highlight very much in tune with the green chemistry movement, is the report of the first aqueous preparation of high yield, relatively monodisperse, well crystallized GaP and InP nanocrystallites, exhibiting pronounced quantum confinement. 59 Whilst they have had to be relegated to ESI, the increasing interest in indium for Barbier-Grignard type organic syntheses in aqueous media has a green complexion and there are the first signs of similar developments for aqueous gallium chemistry. 110b New work on the two-electron transfer for Tl aq 3ϩ /Tl aq ϩ with electrochemical evidence for [Tl()-Tl()] 4ϩ is a major highlight for thallium chemistry. 142 The synthesis and structure of [In()-In()] 4ϩ is also notable. 129 * Electronic supplementary information (ESI) available. See

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Na30.5AgxGa60—x: A Three-Dimensional Network Composed of Ga3, Ga12, and Ga18 Clusters

Abstract: Single crystal X-ray structural determinations for

Cited by 8 publications

References 22 publications

Electronic Stabilization Effects: Three New K−In−T (T = Mg, Au, Zn) Network Compounds

Electronic Stabilization Effects: Three New K−In−T (T = Mg, Au, Zn) Network Compounds

Lithiation-Induced Zinc Clustering of Zn₃, Zn₁₂, and Zn₁₈ Units in Zintl-Like Ca_∼30Li_3+xZn_60–x (x = 0.44–1.38)

4 Aluminium, gallium, indium, and thallium

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Na30.5AgxGa60—x: A Three-Dimensional Network Composed of Ga3, Ga12, and Ga18 Clusters

Abstract: Single crystal X-ray structural determinations for

Cited by 8 publications

References 22 publications

Electronic Stabilization Effects: Three New K−In−T (T = Mg, Au, Zn) Network Compounds

Electronic Stabilization Effects: Three New K−In−T (T = Mg, Au, Zn) Network Compounds

Lithiation-Induced Zinc Clustering of Zn3, Zn12, and Zn18 Units in Zintl-Like Ca∼30Li3+xZn60–x (x = 0.44–1.38)

4 Aluminium, gallium, indium, and thallium

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Lithiation-Induced Zinc Clustering of Zn₃, Zn₁₂, and Zn₁₈ Units in Zintl-Like Ca_∼30Li_3+xZn_60–x (x = 0.44–1.38)