R3Au9Pn (R = Y, Gd–Tm; Pn = Sb, Bi): A Link between Cu10Sn3 and Gd14Ag51
Abstract
A new series of intermetallic compounds R3Au9Pn (R = Y, Gd–Tm; Pn = Sb, Bi) has been discovered during the explorations of the Au-rich parts of rare-earth-containing ternary systems with p-block elements. The existence of the series is strongly restricted by both geometric and electronic factors. R3Au9Pn compounds crystallize in the hexagonal crystal system with space group P63/m (a = 8.08–8.24 Å, c = 8.98–9.08 Å). All compounds feature Au-Pn, formally anionic, networks built up by layers of alternating edge-sharing Au@Au6 and Sb@Au6 trigonal antiprisms of overall composition Au6/2Pn connected through additional Au atoms and separated by a triangular cationic substructure formed by R atoms. From a first look, the series appears to be isostructural with recently reported R3Au7Sn3 (a ternary ordered derivative of the Cu10Sn3-structure type), but no example of R3Au9M is known when M is a triel or tetrel element. R3Au9Pn also contains Au@Au6Au2R3 fully capped trigonal prisms, which are found to be isostructural with those found in the well-researched R14Au51 series. This structural motif, not present in R3Au7Sn3, represents a previously unrecognized link between Cu10Sn3 and Gd14Ag51 parent structure types. Magnetic property measurements carried out for Ho3Au9Sb reveal a complex magnetic structure characterized by antiferromagnetic interactions atmore »
- Authors:
- Publication Date:
- Research Org.:
- Iowa State Univ., Ames, IA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1361562
- Alternate Identifier(s):
- OSTI ID: 1372223
- Grant/Contract Number:
- AC02-07CH11358
- Resource Type:
- Published Article
- Journal Name:
- Inorganic Chemistry
- Additional Journal Information:
- Journal Name: Inorganic Chemistry; Journal ID: ISSN 0020-1669
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Celania, Chris, Smetana, Volodymyr, Provino, Alessia, Pecharsky, Vitalij, Manfrinetti, Pietro, and Mudring, Anja-Verena. R3Au9Pn (R = Y, Gd–Tm; Pn = Sb, Bi): A Link between Cu10Sn3 and Gd14Ag51. United States: N. p., 2017.
Web. doi:10.1021/acs.inorgchem.7b00898.
Celania, Chris, Smetana, Volodymyr, Provino, Alessia, Pecharsky, Vitalij, Manfrinetti, Pietro, & Mudring, Anja-Verena. R3Au9Pn (R = Y, Gd–Tm; Pn = Sb, Bi): A Link between Cu10Sn3 and Gd14Ag51. United States. https://doi.org/10.1021/acs.inorgchem.7b00898
Celania, Chris, Smetana, Volodymyr, Provino, Alessia, Pecharsky, Vitalij, Manfrinetti, Pietro, and Mudring, Anja-Verena. Mon .
"R3Au9Pn (R = Y, Gd–Tm; Pn = Sb, Bi): A Link between Cu10Sn3 and Gd14Ag51". United States. https://doi.org/10.1021/acs.inorgchem.7b00898.
@article{osti_1361562,
title = {R3Au9Pn (R = Y, Gd–Tm; Pn = Sb, Bi): A Link between Cu10Sn3 and Gd14Ag51},
author = {Celania, Chris and Smetana, Volodymyr and Provino, Alessia and Pecharsky, Vitalij and Manfrinetti, Pietro and Mudring, Anja-Verena},
abstractNote = {A new series of intermetallic compounds R3Au9Pn (R = Y, Gd–Tm; Pn = Sb, Bi) has been discovered during the explorations of the Au-rich parts of rare-earth-containing ternary systems with p-block elements. The existence of the series is strongly restricted by both geometric and electronic factors. R3Au9Pn compounds crystallize in the hexagonal crystal system with space group P63/m (a = 8.08–8.24 Å, c = 8.98–9.08 Å). All compounds feature Au-Pn, formally anionic, networks built up by layers of alternating edge-sharing Au@Au6 and Sb@Au6 trigonal antiprisms of overall composition Au6/2Pn connected through additional Au atoms and separated by a triangular cationic substructure formed by R atoms. From a first look, the series appears to be isostructural with recently reported R3Au7Sn3 (a ternary ordered derivative of the Cu10Sn3-structure type), but no example of R3Au9M is known when M is a triel or tetrel element. R3Au9Pn also contains Au@Au6Au2R3 fully capped trigonal prisms, which are found to be isostructural with those found in the well-researched R14Au51 series. This structural motif, not present in R3Au7Sn3, represents a previously unrecognized link between Cu10Sn3 and Gd14Ag51 parent structure types. Magnetic property measurements carried out for Ho3Au9Sb reveal a complex magnetic structure characterized by antiferromagnetic interactions at low temperature (TN = 10 K). Two metamagnetic transitions occur at high field with a change from antiferromagnetic toward ferromagnetic ordering. Density functional theory based computations were performed to understand the materials’ properties and to shed some light on the stability ranges. As a result, this allowed a better understanding of the bonding pattern, especially of the Au-containing substructure, and elucidation of the role of the third element in the stability of the structure type.},
doi = {10.1021/acs.inorgchem.7b00898},
journal = {Inorganic Chemistry},
number = ,
volume = ,
place = {United States},
year = {Mon Jun 05 00:00:00 EDT 2017},
month = {Mon Jun 05 00:00:00 EDT 2017}
}
https://doi.org/10.1021/acs.inorgchem.7b00898
Web of Science
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Works referenced in this record:
Atomic Interactions in the p-Type Clathrate I Ba 8 Au 5.3 Ge 40.7
journal, February 2011
- Zhang, Hui; Borrmann, Horst; Oeschler, Niels
- Inorganic Chemistry, Vol. 50, Issue 4
Generalized Gradient Approximation Made Simple
journal, October 1996
- Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
- Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
Minimal basis sets in the linear muffin-tin orbital method: Application to the diamond-structure crystals C, Si, and Ge
journal, August 1986
- Lambrecht, Walter R. L.; Andersen, O. K.
- Physical Review B, Vol. 34, Issue 4
Cation-Poor Complex Metallic Alloys in Ba(Eu)–Au–Al(Ga) Systems: Identifying the Keys that Control Structural Arrangements and Atom Distributions at the Atomic Level
journal, October 2015
- Smetana, Volodymyr; Steinberg, Simon; Mudryk, Yaroslav
- Inorganic Chemistry, Vol. 54, Issue 21
An empirical correction for absorption anisotropy
journal, January 1995
- Blessing, R. H.
- Acta Crystallographica Section A Foundations of Crystallography, Vol. 51, Issue 1
Three Alkali-Metal–Gold–Gallium Systems. Ternary Tunnel Structures and Some Problems with Poorly Ordered Cations
journal, April 2012
- Smetana, Volodymyr; Miller, Gordon J.; Corbett, John D.
- Inorganic Chemistry, Vol. 51, Issue 14
Projector augmented-wave method
journal, December 1994
- Blöchl, P. E.
- Physical Review B, Vol. 50, Issue 24, p. 17953-17979
Eine neue verbindung im system rubidium-gold: synthese und struktur von Rb3Au7
journal, September 1993
- Zachwieja, Uwe
- Journal of Alloys and Compounds, Vol. 199, Issue 1-2
The quadrupole moment of the 3∕2+ nuclear ground state of Au197 from electric field gradient relativistic coupled cluster and density-functional theory of small molecules and the solid state
journal, March 2005
- Schwerdtfeger, Peter; Bast, Radovan; Gerry, Michael C. L.
- The Journal of Chemical Physics, Vol. 122, Issue 12
Sr2Au6Al3 and Eu2Au6Al3 – First Representatives of the Sr2Au6Zn3 Type with Aluminum Triangles
journal, January 2014
- Gerke, Birgit; Pöttgen, Rainer
- Zeitschrift für Naturforschung B, Vol. 69, Issue 1
Cs4Au7Sn2: eine Gold–Zinn-Gerüststruktur mit [Au7]-Clustern und Sn2-Hanteln
journal, September 1998
- Zachwieja, Uwe; Wlodarski, Jörg
- Zeitschrift für anorganische und allgemeine Chemie, Vol. 624, Issue 9
Turning Gold into “Diamond”: A Family of Hexagonal Diamond-Type Au-Frameworks Interconnected by Triangular Clusters in the Sr–Al–Au System
journal, February 2014
- Palasyuk, Andriy; Grin, Yuri; Miller, Gordon J.
- Journal of the American Chemical Society, Vol. 136, Issue 8
From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999
- Kresse, G.; Joubert, D.
- Physical Review B, Vol. 59, Issue 3, p. 1758-1775
Explicit, First-Principles Tight-Binding Theory
journal, December 1984
- Andersen, O. K.; Jepsen, O.
- Physical Review Letters, Vol. 53, Issue 27
Cesiumauride Ammonia (1/1), CsAu⋅NH3: A Crystalline Analogue to Alkali Metals Dissolved in Ammonia?
journal, January 2002
- Mudring, Anja-Verena; Jansen, Martin; Daniels, Jörg
- Angewandte Chemie International Edition, Vol. 41, Issue 1
Approximant Phases and an Icosahedral Quasicrystal in the Ca−Au−Ga System: The Influence of Size of Gallium versus Indium
journal, September 2008
- Lin, Qisheng; Corbett, John D.
- Inorganic Chemistry, Vol. 47, Issue 17
Zn 3 and Ga 3 Triangles as Building Units in Sr 2 Au 6 Zn 3 and Sr 2 Au 6 Ga 3 : Zn
journal, September 2013
- Gerke, Birgit; Hoffmann, Rolf-Dieter; Pöttgen, Rainer
- Zeitschrift für anorganische und allgemeine Chemie, Vol. 639, Issue 14
Ca 14 Au 46 Sn 5 : a “Colored” Gd 14 Ag 51 -Type Structure Containing Columns of Well-Differentiated Hexagonal Gold Stars
journal, March 2011
- Lin, Qisheng; Corbett, John D.
- Inorganic Chemistry, Vol. 50, Issue 5
Relativity and the periodic system of elements
journal, August 1979
- Pyykko, Pekka; Desclaux, Jean Paul
- Accounts of Chemical Research, Vol. 12, Issue 8
Gold in the Layered Structures of R 3 Au 7 Sn 3 : From Relativity to Versatility
journal, September 2016
- Provino, Alessia; Steinberg, Simon; Smetana, Volodymyr
- Crystal Growth & Design, Vol. 16, Issue 10
Relativistic effects on chemical properties
journal, August 1979
- Pitzer, Kenneth S.
- Accounts of Chemical Research, Vol. 12, Issue 8
Einkristallzüchtung und Strukturverfeinerung von KAu5 und RbAu5
journal, May 1993
- Zachwieja, U.
- Journal of Alloys and Compounds, Vol. 196, Issue 1-2
Ab initiomolecular dynamics for liquid metals
journal, January 1993
- Kresse, G.; Hafner, J.
- Physical Review B, Vol. 47, Issue 1, p. 558-561
Kristallstruktur von Cu10Sn3(m)
journal, January 1971
- Lenz, J.; Schubert, K.
- Monatshefte f�r Chemie, Vol. 102, Issue 6
Base-Induced Disproportionation of Elemental Gold
journal, September 2000
- Mudring, Anja-Verena; Jansen, Martin
- Angewandte Chemie, Vol. 39, Issue 17
New ternary phases from the R–Au–Ga systems (R = Gd-Tm)
journal, January 2014
- Verbovytskyy, Yuriy
- Chemistry of Metals and Alloys, Vol. 7, Issue 1/2
Relativistic Effects in Chemistry: More Common Than You Thought
journal, May 2012
- Pyykkö, Pekka
- Annual Review of Physical Chemistry, Vol. 63, Issue 1
Covalent radii revisited
journal, January 2008
- Cordero, Beatriz; Gómez, Verónica; Platero-Prats, Ana E.
- Dalton Transactions, Issue 21
Antiferromagnetic three-sublattice Tb ordering in
journal, October 2005
- Fischer, P.; Pomjakushin, V.; Keller, L.
- Physical Review B, Vol. 72, Issue 13
Crystal Structure and Bonding in BaAu 5 Ga 2 and AeAu 4+ x Ga 3– x (Ae = Ba and Eu): Hexagonal Diamond-Type Au Frameworks and Remarkable Cation/Anion Partitioning in the Ae–Au–Ga Systems
journal, November 2014
- Smetana, Volodymyr; Steinberg, Simon; Card, Nathan
- Inorganic Chemistry, Vol. 54, Issue 3
The structure type and its relation to some complex amalgam structures
journal, January 2015
- Tambornino, Frank; Sappl, Jonathan; Hoch, Constantin
- Journal of Alloys and Compounds, Vol. 618
A short history of SHELX
journal, December 2007
- Sheldrick, George M.
- Acta Crystallographica Section A Foundations of Crystallography, Vol. 64, Issue 1, p. 112-122
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996
- Kresse, G.; Furthmüller, J.
- Computational Materials Science, Vol. 6, Issue 1, p. 15-50
R(Au∼0.75Sb∼0.25)2 (R=La, Ce, Pr) with UHg2 structure type, new members of the AlB2 family
journal, February 2007
- Salamakha, L. P.; Sologub, O. L.; Gonçalves, A. P.
- Journal of Alloys and Compounds, Vol. 429, Issue 1-2
Hexagonal-Diamond-like Gold Lattices, Ba and (Au,T) 3 Interstitials, and Delocalized Bonding in a Family of Intermetallic Phases Ba 2 Au 6 (Au,T) 3 (T = Zn, Cd, Ga, In, or Sn)
journal, July 2013
- Lin, Qisheng; Mishra, Trinath; Corbett, John D.
- Journal of the American Chemical Society, Vol. 135, Issue 30
Infinite Gold Zig-Zag Chains as Structural Motif in Ca3Au3In – A Ternary Ordered Variant of the Ni4B3 Type
journal, January 2008
- Muts, Ihor R.; Zaremba, Vasyl I.; Rodewald, Ute Ch.
- Zeitschrift für anorganische und allgemeine Chemie, Vol. 634, Issue 1
A Sodium-Containing Quasicrystal: Using Gold To Enhance Sodium’s Covalency in Intermetallic Compounds
journal, November 2012
- Smetana, Volodymyr; Lin, Qisheng; Pratt, Daniel K.
- Angewandte Chemie International Edition, Vol. 51, Issue 51
Four Polyanionic Compounds in the K–Au–Ga System: A Case Study in Exploratory Synthesis and of the Art of Structural Analysis
journal, January 2012
- Smetana, Volodymyr; Corbett, John D.; Miller, Gordon J.
- Inorganic Chemistry, Vol. 51, Issue 3
Relativistic effects in structural chemistry
journal, May 1988
- Pyykko, Pekka
- Chemical Reviews, Vol. 88, Issue 3
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996
- Kresse, G.; Furthmüller, J.
- Physical Review B, Vol. 54, Issue 16, p. 11169-11186
Ternary stannides RE2Au5Sn2 (RE = Gd-Er) – i3 superstructures of the Fe2P type
journal, January 2015
- Fickenscher, Thomas; Rodewald, Ute Ch.; Pöttgen, Rainer
- Zeitschrift für Kristallographie - Crystalline Materials, Vol. 230, Issue 2
Syntheses optimization, structural and thermoelectric properties of 1/1 Tsai-type quasicrystal approximants in RE–Au–SM systems (RE=Yb, Gd and SM=Si, Ge)
journal, March 2013
- Gebresenbut, Girma Hailu; Tamura, Ryuji; Eklöf, Daniel
- Journal of Physics: Condensed Matter, Vol. 25, Issue 13
Density functional theory investigation of gold cluster geometry and gas-phase reactivity with O2
journal, December 2002
- Wells, David H.; Delgass, W. Nicholas; Thomson, Kendall T.
- The Journal of Chemical Physics, Vol. 117, Issue 23
Development of the Ca−Au−In Icosahedral Quasicrystal and Two Crystalline Approximants: Practice via Pseudogap Electronic Tuning
journal, May 2007
- Lin, Qisheng; Corbett, John D.
- Journal of the American Chemical Society, Vol. 129, Issue 21
Gold-rich R 3 Au 7 Sn 3 : establishing the interdependence between electronic features and physical properties
journal, January 2015
- Provino, Alessia; Steinberg, Simon; Smetana, Volodymyr
- J. Mater. Chem. C, Vol. 3, Issue 32
Polyclusters and Substitution Effects in the Na–Au–Ga System: Remarkable Sodium Bonding Characteristics in Polar Intermetallics
journal, October 2013
- Smetana, Volodymyr; Miller, Gordon J.; Corbett, John D.
- Inorganic Chemistry, Vol. 52, Issue 21
Synthese und Struktur von K 2 Au 3 , einer neuen Phase im System Kalium—Gold / Synthesis and Structure of K 2 Au 3 , a New Phase in the System Potassium —Gold
journal, February 1989
- Krieger-Beck, Petra; Brodbeck, Andreas; Strähle, Joachim
- Zeitschrift für Naturforschung B, Vol. 44, Issue 2
Rb4Au7Sn2, eine intermetallische Phase mit siebenatomigen Goldclustern/ Rb4Au7Sn2, an Intermetallic Phase with Sevenatomic Gold-Clusters
journal, July 1981
- Sinnen, Heinz-Dieter; Schuster, Hans-Uwe
- Zeitschrift für Naturforschung B, Vol. 36, Issue 7
SrAu4Ga3: a further example with Ga3 units and a Lonsdaleite-related gold substructure
journal, April 2014
- Seidel, Stefan; Hoffmann, Rolf-Dieter; Pöttgen, Rainer
- Monatshefte für Chemie - Chemical Monthly, Vol. 145, Issue 7
Magnetocaloric Behavior in Ternary Europium Indides EuT 5 In: Probing the Design Capability of First-Principles-Based Methods on the Multifaceted Magnetic Materials
journal, November 2016
- Bigun, Inna; Steinberg, Simon; Smetana, Volodymyr
- Chemistry of Materials, Vol. 29, Issue 6
Einige strukturelle Ergebnisse an metallischen Phasen IV
journal, January 1959
- Schubert, K.; Balk, M.; Bhan, S.
- Die Naturwissenschaften, Vol. 46, Issue 23
Improved tetrahedron method for Brillouin-zone integrations
journal, June 1994
- Blöchl, Peter E.; Jepsen, O.; Andersen, O. K.
- Physical Review B, Vol. 49, Issue 23
Hypervalent Bonding in One, Two, and Three Dimensions: Extending the Zintl-Klemm Concept to Nonclassical Electron-Rich Networks
journal, July 2000
- A. Papoian, Garegin; Hoffmann, Roald
- Angewandte Chemie International Edition, Vol. 39, Issue 14
Triangular Zn 3 and Ga 3 units in Sr 2 Au 6 Zn 3 , Eu 2 Au 6 Zn 3 , Sr 2 Au 6 Ga 3 , and Eu 2 Au 6 Ga 3 – structure, magnetism, 151 Eu Mössbauer and 69;71 Ga solid state NMR spectroscopy
journal, March 2016
- Gerke, Birgit; Korthaus, Alexander; Niehaus, Oliver
- Zeitschrift für Naturforschung B, Vol. 71, Issue 5
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