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Title: Gold–Gold Bonding: The Key to Stabilizing the 19-Electron Ternary Phases LnAuSb (Ln = La–Nd and Sm)

Authors:
; ; ; ; ; ; ;  [1]
  1. (Princeton)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Sponsoring Org.:
U.S. AIR FORCE- OFFICE OF SCIENTIFIC RESEARCH
OSTI Identifier:
1169348
Resource Type:
Journal Article
Resource Relation:
Journal Name: J. Am. Chem. Soc.; Journal Volume: 137; Journal Issue: (3) ; 01, 2015
Country of Publication:
United States
Language:
ENGLISH

Citation Formats

Seibel, Elizabeth M., Schoop, Leslie M., Xie, Weiwei, Gibson, Quinn D., Webb, James B., Fuccillo, Michael K., Krizan, Jason W., and Cava, Robert J. Gold–Gold Bonding: The Key to Stabilizing the 19-Electron Ternary Phases LnAuSb (Ln = La–Nd and Sm). United States: N. p., 2016. Web. doi:10.1021/ja511394q.
Seibel, Elizabeth M., Schoop, Leslie M., Xie, Weiwei, Gibson, Quinn D., Webb, James B., Fuccillo, Michael K., Krizan, Jason W., & Cava, Robert J. Gold–Gold Bonding: The Key to Stabilizing the 19-Electron Ternary Phases LnAuSb (Ln = La–Nd and Sm). United States. doi:10.1021/ja511394q.
Seibel, Elizabeth M., Schoop, Leslie M., Xie, Weiwei, Gibson, Quinn D., Webb, James B., Fuccillo, Michael K., Krizan, Jason W., and Cava, Robert J. Wed . "Gold–Gold Bonding: The Key to Stabilizing the 19-Electron Ternary Phases LnAuSb (Ln = La–Nd and Sm)". United States. doi:10.1021/ja511394q.
@article{osti_1169348,
title = {Gold–Gold Bonding: The Key to Stabilizing the 19-Electron Ternary Phases LnAuSb (Ln = La–Nd and Sm)},
author = {Seibel, Elizabeth M. and Schoop, Leslie M. and Xie, Weiwei and Gibson, Quinn D. and Webb, James B. and Fuccillo, Michael K. and Krizan, Jason W. and Cava, Robert J.},
abstractNote = {},
doi = {10.1021/ja511394q},
journal = {J. Am. Chem. Soc.},
number = (3) ; 01, 2015,
volume = 137,
place = {United States},
year = {Wed Jun 15 00:00:00 EDT 2016},
month = {Wed Jun 15 00:00:00 EDT 2016}
}
  • The new title compounds were prepared by reaction of the elemental components at high temperatures. They crystallize with a rhombohedral cell in space group R 3m. The structure was determined for Pr/sub 2/Mn/sub 17/C/sub 3-x/ (x = 1.23), which has the lattice constants a = 8.8714 (7) A and c = 12.783 (2) A with Z = 3 formula units in the hexagonal setting of the cell. The structure refinement from single-crystal X-ray data resulted in a residual of R = 0.023 for 25 variable parameters and 414 unique structure factors. The Pr and Mn positions correspond to those ofmore » the Th and Zn positions in Th/sub 2/Zn/sub 17/. The carbon atoms fill voids of nearly octahedral shape formed by a rectangle of Mn atoms (Mn-C distances 1.94 and 1.95 A) and two Pr atoms at 2.57 A. The idealized composition with all octahedral voids filled is Pr/sub 2/Mn/sub 17/C/sub 3/. The refinement of the occupancy parameter for this position resulted in a value of 59 +/- 3% for the crystal used for the structure determination. The discussion reviews the correspondence of binary intermetallic and ternary complex carbide phases. 28 references, 2 figures, 5 tables.« less
  • The structures of two new complex copper oxide phases refined from powder neutron diffraction data are reported. LaNdSrCu{sub 2}O{sub 6} is isostructural with La{sub 2}SrCu{sub 2}O{sub 6} but shows an unusual ordering of Nd and La over the perovskite-type A sites. Nd{sub 1.4}Sr{sub 1.6}Cu{sub 2}O{sub 5.79} has a structure based on a tripled (a {times} 3a {times} c). The lattice parameters and oxygen stoichiometries of a number of new phases of both structure types are presented.
  • The synthesis and structure of triple layered Bi{sub 2}Ln{sub 2}Ti{sub 3}O{sub 12} Aurivillius phases (Ln=La, Pr, Nd and Sm), prepared from K{sub 2}Ln{sub 2}Ti{sub 3}O{sub 10} Ruddlesden-Popper precursors, has been investigated. These materials adopt a body centred tetragonal structure (space group I4/mmm, with unit cell parameters a{approx}3.8 A and c{approx}33 A) comprising a regular intergrowth of [Bi{sub 2}O{sub 2}]{sup 2+} fluorite-type and [Ln{sub 2}Ti{sub 3}O{sub 10}]{sup 2-} perovskite-type layers. A significant degree of cation disorder is present in the Bi{sub 2}Ln{sub 2}Ti{sub 3}O{sub 12} system, involving the cross-substitution of Ln/Bi cations onto the Bi/Ln sites in the fluorite- and perovskite-typemore » layers, respectively. As the size of the lanthanide cation is reduced, Bi/Ln disorder is significantly suppressed due to the effect of bond length mismatch in the perovskite-type layer in the crystal structure of Bi{sub 2}Ln{sub 2}Ti{sub 3}O{sub 12}. This offers a potential strategy for the chemical control of cation disorder in the Bi{sub 2}Ln{sub 2}Ti{sub 3}O{sub 12} system.« less
  • The quaternary oxychalcogenides Ln{sub 4}MnOSe{sub 6} (Ln=La, Ce, Nd), Ln{sub 4}FeOSe{sub 6} (Ln=La, Ce, Sm), and La{sub 4}MnOS{sub 6} have been synthesized by the reactions of Ln (Ln=La, Ce, Nd, Sm), M (M=Mn, Fe), Se, and SeO{sub 2} at 1173K for the selenides or by the reaction of La{sub 2}S{sub 3} and MnO at 1173K for the sulfide. Warning: These reactions frequently end in explosions. These isostructural compounds crystallize with two formula units in space group C{sub 6v}{sup 4}-P6{sub 3}mc of the hexagonal system. The cell constants (a, c in A) at 153K are: La{sub 4}MnOSe{sub 6}, 9.7596(3), 7.0722(4); La{submore » 4}FeOSe{sub 6}, 9.7388(4), 7.0512(5); Ce{sub 4}MnOSe{sub 6}, 9.6795(4), 7.0235(5); Ce{sub 4}FeOSe{sub 6}, 9.6405(6), 6.9888(4); Nd{sub 4}MnOSe{sub 6}, 9.5553(5), 6.9516(5); Sm{sub 4}FeOSe{sub 6}, 9.4489(5), 6.8784(5); and La{sub 4}MnOS{sub 6}, 9.4766(6), 6.8246(6). The structure of these Ln{sub 4}MOQ{sub 6} compounds comprises a three-dimensional framework of interconnected LnOQ{sub 7} bicapped trigonal prisms, MQ{sub 6} octahedra, and the unusual LnOQ{sub 6} tricapped tetrahedra.« less
  • The authors investigate one of the primary physical parameters of compounds of the title type such as the width of the band gap, and discuss the results based on the structure of the shell of r.e.e. atoms. In the title compounds, the width of the band gap decreases upon transition from lanthanum to cerium both for the sulfides and selenides, and the tellurides.