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Title: Ternary Polar Intermetallics within the Pt/Sn/R Systems (R = La–Sm): Stannides or Platinides?

Abstract

Starting generally with a 4:6:3 molar ratio of Pt, Sn, and R (where R = La–Sm), with or without the application of a NaCl flux, seven ternary compounds were obtained as single crystals. The platinides Pt4Sn6R3 (R = La–Nd) crystallize with the Pt4Ge6Pr3 type of structure (oP52, Pnma, a = 27.6–27.8 Å, b = 4.59–4.64 Å, c = 9.33–9.40 Å). With R = Pr, Pt4Sn6Pr3–x (oP52, Pnma, a = 7.2863(3) Å, b = 4.4909(2) Å, c = 35.114(1) Å) is also obtained, which might be considered a high-temperature polymorph with disorder on the Sn- and Pr-sites. For R = Nd and Sm, a structurally related isostructural series with a slightly different composition Pt3Sn5R2–x (oP52, Cmc21, a = 4.50–4.51 Å, b = 26.14–26.30 Å, c ≈ 7.29 Å) has been observed, together with Pt7Sn9Sm5 (oS42, Amm2, a = 4.3289(5) Å, b = 28.798(4) Å, c = 7.2534(9) Å) under the same conditions. The latter exhibits the rare Zr5Pd9P7-type structure, linking polar intermetallics to metal phosphides, in accord with P7Pd9Zr5≡Pt7Sn9Sm5. Finally, all structures may be described in terms of either negative Pt/Sn networks encapsulating positive R atoms, or {PtSnx} clusters (x = 5, 6, or rarely 7) sharing vertices and edges withmore » R in the second coordination sphere and with considerable heterometallic Pt–R bonding contributions.« less

Authors:
 [1]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [1]
  1. Department of Chemistry, Iowa State University, Ames, Iowa 50011, United States, Ames Laboratory, USDOE, Iowa State University, Ames, Iowa 50011, United States
  2. Ames Laboratory, USDOE, Iowa State University, Ames, Iowa 50011, United States, Department of Materials and Environmental Chemistry, Stockholm University, Svante Arrhenius väg 16 C, 10691 Stockholm, Sweden
  3. Ames Laboratory, USDOE, Iowa State University, Ames, Iowa 50011, United States, Department of Materials and Environmental Chemistry, Stockholm University, Svante Arrhenius väg 16 C, 10691 Stockholm, Sweden, Department of Materials Science and Engineering, Iowa State University, Ames, Iowa 50011, United States
Publication Date:
Research Org.:
Ames Lab., Ames, IA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division
OSTI Identifier:
1617547
Alternate Identifier(s):
OSTI ID: 1630910
Report Number(s):
IS-J-10,218
Journal ID: ISSN 0020-1669
Grant/Contract Number:  
AC02-07CH11358; 46595
Resource Type:
Published Article
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Name: Inorganic Chemistry Journal Volume: 59 Journal Issue: 10; 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; chemical structure; platinum; cluster chemistry; crystal structure; intermetallics

Citation Formats

Rhodehouse, Melissa L., Smetana, Volodymyr, Celania, Chris, Mudring, Anja-Verena, and Meyer, Gerd H. Ternary Polar Intermetallics within the Pt/Sn/R Systems (R = La–Sm): Stannides or Platinides?. United States: N. p., 2020. Web. doi:10.1021/acs.inorgchem.0c00884.
Rhodehouse, Melissa L., Smetana, Volodymyr, Celania, Chris, Mudring, Anja-Verena, & Meyer, Gerd H. Ternary Polar Intermetallics within the Pt/Sn/R Systems (R = La–Sm): Stannides or Platinides?. United States. doi:https://doi.org/10.1021/acs.inorgchem.0c00884
Rhodehouse, Melissa L., Smetana, Volodymyr, Celania, Chris, Mudring, Anja-Verena, and Meyer, Gerd H. Thu . "Ternary Polar Intermetallics within the Pt/Sn/R Systems (R = La–Sm): Stannides or Platinides?". United States. doi:https://doi.org/10.1021/acs.inorgchem.0c00884.
@article{osti_1617547,
title = {Ternary Polar Intermetallics within the Pt/Sn/R Systems (R = La–Sm): Stannides or Platinides?},
author = {Rhodehouse, Melissa L. and Smetana, Volodymyr and Celania, Chris and Mudring, Anja-Verena and Meyer, Gerd H.},
abstractNote = {Starting generally with a 4:6:3 molar ratio of Pt, Sn, and R (where R = La–Sm), with or without the application of a NaCl flux, seven ternary compounds were obtained as single crystals. The platinides Pt4Sn6R3 (R = La–Nd) crystallize with the Pt4Ge6Pr3 type of structure (oP52, Pnma, a = 27.6–27.8 Å, b = 4.59–4.64 Å, c = 9.33–9.40 Å). With R = Pr, Pt4Sn6Pr3–x (oP52, Pnma, a = 7.2863(3) Å, b = 4.4909(2) Å, c = 35.114(1) Å) is also obtained, which might be considered a high-temperature polymorph with disorder on the Sn- and Pr-sites. For R = Nd and Sm, a structurally related isostructural series with a slightly different composition Pt3Sn5R2–x (oP52, Cmc21, a = 4.50–4.51 Å, b = 26.14–26.30 Å, c ≈ 7.29 Å) has been observed, together with Pt7Sn9Sm5 (oS42, Amm2, a = 4.3289(5) Å, b = 28.798(4) Å, c = 7.2534(9) Å) under the same conditions. The latter exhibits the rare Zr5Pd9P7-type structure, linking polar intermetallics to metal phosphides, in accord with P7Pd9Zr5≡Pt7Sn9Sm5. Finally, all structures may be described in terms of either negative Pt/Sn networks encapsulating positive R atoms, or {PtSnx} clusters (x = 5, 6, or rarely 7) sharing vertices and edges with R in the second coordination sphere and with considerable heterometallic Pt–R bonding contributions.},
doi = {10.1021/acs.inorgchem.0c00884},
journal = {Inorganic Chemistry},
number = 10,
volume = 59,
place = {United States},
year = {2020},
month = {5}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: https://doi.org/10.1021/acs.inorgchem.0c00884

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