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Title: 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 » 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.« less

Authors:
; ORCiD logo; ORCiD logo; ; ; ORCiD logo
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}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1021/acs.inorgchem.7b00898

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Cited by: 8 works
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Figures / Tables:

Table 1 Table 1: Crystallographic Details and Refinement Parameters for Y3Au9Sb, Gd3Au9Sb, Dy3Au9Sb, and Gd3Au9Bi

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