Ternary Polar Intermetallics within the Pt/Sn/R Systems (R = La–Sm): Stannides or Platinides?
- Department of Chemistry, Iowa State University, Ames, Iowa 50011, United States, Ames Laboratory, USDOE, Iowa State University, Ames, Iowa 50011, United States
- 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
- 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
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.
- Research Organization:
- Ames Laboratory (AMES), Ames, IA (United States)
- Sponsoring Organization:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division
- Grant/Contract Number:
- AC02-07CH11358; 46595
- OSTI ID:
- 1617547
- Alternate ID(s):
- OSTI ID: 1630910
- Report Number(s):
- IS-J-10,218
- Journal Information:
- Inorganic Chemistry, Journal Name: Inorganic Chemistry Vol. 59 Journal Issue: 10; ISSN 0020-1669
- Publisher:
- American Chemical Society (ACS)Copyright Statement
- Country of Publication:
- United States
- Language:
- English
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