Li14.7Mg36.8Cu21.5Ga66: An Intermetallic Representative of a Type IV Clathrate

Lin, Qisheng; Corbett, John D.

doi:10.1021/ic8003245

Cited by 15 publications

(9 citation statements)

References 32 publications

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“…Although ten clathrate types of crystal structure have been reported in the literature, the vast majority of inorganic clathrates crystallize with the type‐I structure, the types‐II, VIII, and IX being moderately represented . On the contrary, types‐III, IV, VII, and X are very rare, whereas types‐V and VI are not known among inorganic clathrates.…”

Section: Introductionmentioning

confidence: 99%

Structure‐Related Thermal Properties of Type‐VII Clathrates SrNi₂P₄ and BaNi₂P₄ at Low Temperature

Новиков

Pilipenko

Matovnikov

et al. 2018

Physica Status Solidi (b)

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Heat capacity C P (T) (2-300 K) and unit cell parameters a(T), b(T), and c(T) (5-300 K) of type-VII clathrates SrNi 2 P 4 and BaNi 2 P 4 have been investigated experimentally. The studied compounds are prepared by a two-stage ampoule synthesis. Diffuse maxima of C P (T) near 5 K along with anomalies in temperature dependencies of unit cell parameters below 10 K are observed and related to the influence of two-level systems in guest-atom substructures. Joint analysis of temperature dependencies of heat capacity and unit cell volume of both clathrates within the frames of the Debye-Einstein model allowed determining characteristic temperatures of the clathrate frameworks and guest atoms as well as parameters of the two-level systems. The relationships of the obtained characteristics and the peculiarities of the crystal structures of SrNi 2 P 4 and BaNi 2 P 4 are discussed.

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Section: Introductionmentioning

confidence: 99%

Structure‐Related Thermal Properties of Type‐VII Clathrates SrNi₂P₄ and BaNi₂P₄ at Low Temperature

Новиков

Pilipenko

Matovnikov

et al. 2018

Physica Status Solidi (b)

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“…For example, we have reported the syntheses, structures, and aspects of the bonding of a series of ACs and evidence of i-QCs in the Sc-Cu-Zn, 27,28 Sc-Mg-Cu-Ga, 29 Sc-MgZn, 30,31 Ca-Au-In, 32 and Ca-Au-Ga 33 ternary systems, with the last four following our pseudogap tuning route. 29 Recently, we found that the YCd 6 -type phases also exist in the M-Au-Ge (M = Ca and Yb) systems, 34 which, for the first time, included the metalloid Ge in YCd 6 -type compounds.…”

Section: Introductionmentioning

confidence: 99%

Development of an Icosahedral Quasicrystal and Two Approximants in the Ca−Au−Sn System: Syntheses and Structural Analyses

Lin

Corbett

2010

Inorg. Chem.

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The realm of Tsai-type (YCd 6 -type) quasicrystals (QCs) and their approximants (ACs) continues to expand to the east in the periodic table. The heavy tetrel Sn is now one of the major components in the new Ca 15.0(5) Au 60.0(4) Sn 25.0(2) (atom %) icosahedral QC and in the corresponding 1/1 and 2/1 ACs. (The 2/1 AC with Yb is also established.) Single-crystal X-ray diffraction on a 1/1 AC gives the refined formula of Ca 3 Au 14.36(3) Sn 4.38(5) in space group Im3, a = 15.131(1) Å , whereas a representative 2/1 AC gives Ca 13 Au 47.2(1) Sn 28.1(1) , Pa3 and a = 24.444(1) Å . Both ACs contain five-shell multiply endohedral triacontahedral clusters as the common building blocks, as in the parent structure of YCd 6 . The 2/1 AC also contains four Ca 2 -dimer-centered prolate rhombohedra (PRs) in the unit cell. The long-range order between triacontahedra and PRs in the 2/1 AC is the same as those in Bergman-type 2/1 ACs. A TB-LMTO-ASA calculation on an ideal 1/1 AC model reveals a shallow pseudogap in the total densities-of-states data around the Fermi energy, as expected. The depth of the pseudogap is considerably enhanced through interactions between the Ca 3d states and s and p states of Au and Sn.

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“…During the exploratory synthesis of quasicrystals, we often encountered novel complex crystalline intermetallics with compositions nearby quasicrystals, e.g., Mg 35 Cu 24 Ga 53 , 22 Sc 4 Mg x Cu 15−x Ga 7.5 , 23 Li 14.7 Mg 36.8 Cu 21.5 Ga 66 ,24 …”

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confidence: 99%

Electron-Poor Polar Intermetallics: Complex Structures, Novel Clusters, and Intriguing Bonding with Pronounced Electron Delocalization

Lin

Miller

2017

Acc. Chem. Res.

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Intermetallic compounds represent an extensive pool of candidates for energy related applications stemming from magnetic, electric, optic, caloric, and catalytic properties. The discovery of novel intermetallic compounds can enhance understanding of the chemical principles that govern structural stability and chemical bonding as well as finding new applications. Valence electron-poor polar intermetallics with valence electron concentrations (VECs) between 2.0 and 3.0 e/atom show a plethora of unprecedented and fascinating structural motifs and bonding features. Therefore, establishing simple structure-bonding-property relationships is especially challenging for this compound class because commonly accepted valence electron counting rules are inappropriate. During our efforts to find quasicrystals and crystalline approximants by valence electron tuning near 2.0 e/atom, we observed that compositions close to those of quasicrystals are exceptional sources for unprecedented valence electron-poor polar intermetallics, e.g., CaAuIn containing (AuIn) wavy layers, LiMgCuGa adopting a type IV clathrate framework, and ScMgCuGa that is incommensurately modulated. In particular, exploratory syntheses of AAuT (A = Ca, Sr, Ba and T = Ge, Sn) phases led to interesting bonding features for Au, such as columns, layers, and lonsdaleite-type tetrahedral frameworks. Overall, the breadth of Au-rich polar intermetallics originates, in part, from significant relativistics effect on the valence electrons of Au, effects which result in greater 6s/5d orbital mixing, a small effective metallic radius, and an enhanced Mulliken electronegativity, all leading to ultimate enhanced binding with nearly all metals including itself. Two other successful strategies to mine electron-poor polar intermetallics include lithiation and "cation-rich" phases. Along these lines, we have studied lithiated Zn-rich compounds in which structural complexity can be realized by small amounts of Li replacing Zn atoms in the parent binary compounds CaZn, CaZn, and CaZn; their phase formation and bonding schemes can be rationalized by Fermi surface-Brillouin zone interactions between nearly free-electron states. "Cation-rich", electron-poor polar intermetallics have emerged using rare earth metals as the electropositive ("cationic") component together metal/metalloid clusters that mimic the backbones of aromatic hydrocarbon molecules, which give evidence of extensive electronic delocalization and multicenter bonding. Thus, we can identify three distinct, valence electron-poor, polar intermetallic systems that have yielded unprecedented phases adopting novel structures containing complex clusters and intriguing bonding characteristics. In this Account, we summarize our recent specific progress in the developments of novel Au-rich BaAl-type related structures, shown in the "gold-rich grid", lithiation-modulated Ca-Li-Zn phases stabilized by different bonding characteristics, and rare earth-rich polar intermetallics containing unprecedented hydrocarbon-like planar Co-Ge...

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Li_14.7Mg_36.8Cu_21.5Ga₆₆: An Intermetallic Representative of a Type IV Clathrate

Abstract: Synthetic explorations in the quaternary Li-Mg-Cu-Ga system yield the novel intermetallic Li 14.7(8)

Cited by 15 publications

References 32 publications

Structure‐Related Thermal Properties of Type‐VII Clathrates SrNi₂P₄ and BaNi₂P₄ at Low Temperature

Structure‐Related Thermal Properties of Type‐VII Clathrates SrNi₂P₄ and BaNi₂P₄ at Low Temperature

Development of an Icosahedral Quasicrystal and Two Approximants in the Ca−Au−Sn System: Syntheses and Structural Analyses

Electron-Poor Polar Intermetallics: Complex Structures, Novel Clusters, and Intriguing Bonding with Pronounced Electron Delocalization

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Li14.7Mg36.8Cu21.5Ga66: An Intermetallic Representative of a Type IV Clathrate

Abstract: Synthetic explorations in the quaternary Li-Mg-Cu-Ga system yield the novel intermetallic Li 14.7(8)

Cited by 15 publications

References 32 publications

Structure‐Related Thermal Properties of Type‐VII Clathrates SrNi2P4 and BaNi2P4 at Low Temperature

Structure‐Related Thermal Properties of Type‐VII Clathrates SrNi2P4 and BaNi2P4 at Low Temperature

Development of an Icosahedral Quasicrystal and Two Approximants in the Ca−Au−Sn System: Syntheses and Structural Analyses

Electron-Poor Polar Intermetallics: Complex Structures, Novel Clusters, and Intriguing Bonding with Pronounced Electron Delocalization

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Li_14.7Mg_36.8Cu_21.5Ga₆₆: An Intermetallic Representative of a Type IV Clathrate

Structure‐Related Thermal Properties of Type‐VII Clathrates SrNi₂P₄ and BaNi₂P₄ at Low Temperature

Structure‐Related Thermal Properties of Type‐VII Clathrates SrNi₂P₄ and BaNi₂P₄ at Low Temperature