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Title: From the Nonexistent Polar Intermetallic Pt 3Pr 4 via Pt 2–xPr 3 to Pt/Sn/Pr Ternaries

Abstract

Here the Pt–Pr phase diagram has been explored well, recent work on rare-earth metal cluster halides with endohedral transition metal atoms has provided a new binary intermetallic that is nonexistent in the known phase diagram: The binary Pt 3Pr 4 ( 1) crystallizes in a new structure type ( mP56, P2 1/c, a = 12.353(2) Å, b = 7.4837(9) Å, c = 17.279(2) Å, β = 118.003(7)°, Z = 8) with six crystallographically independent Pt as well as eight Pr positions. The subsequent detailed investigation has led to another previously unreported, binary phase with the Ga 2Gd 3 structure type, Pt 2–xPr 3 ( 2, tI80, I4/ mcm, a = 11.931(9) Å, c = 14.45(1) Å, Z = 16), that is practically overlapping with the rhombohedral Pt 2Pr 3 existing in the phase diagram. Application of different tin containing fluxes to reproduce the newly detected phases brought about two almost iso-compositional ternary compounds with Sn, Pt 4Sn 6Pr 2.91 ( 3), and Pt 4Sn 6Pr 3 ( 4), as well as Pt 12Sn 24Pr 4.84 ( 5). 3 is a representative of the Pt 4Ge 6Ce 3 type ( oP52, Pnma, a = 7.2863(3) Å, b = 4.4909(2) Å, c = 35.114(2) Å), while 4 represents a new variant of the prolific T 4 E 6 R 3 family (T = transition metal, E = main group (semi)metal, R = rare-earth metal; Pt 4Sn 6Pr 3: oP52, Pnma, a = 27.623(1) Å, b = 4.5958(2) Å, c = 9.3499(5) Å). Pt 12Sn 24Pr 5–x ( 5) crystallizes as a variant of the Ni 8Sn 16Gd 3 type ( cI82, Im$$\bar{3}$$, a = 12.274(1) Å, Z = 2). Electronic structure calculations provide hints on the origin of the structural changes (pseudo-polymorphism) for Pt xPr 3 with x = 1.97 and 2.00, respectively, and reveal that heteroatomic Pt–Pr bonding strongly dominates in both binaries while the addition of the reactive metal tin leads to dominating Pt–Sn bonding interactions in the ternaries; Pt–Pt bonding interactions are strong but represent a minority in the binaries and are not present at all in the ternaries.

Authors:
 [1];  [2]; ORCiD logo [3]; ORCiD logo [3]; ORCiD logo [4]
  1. Ames Lab. and Iowa State Univ., Ames, IA (United States)
  2. Univ. zu Koln, Koln (Germany)
  3. Ames Lab. and Iowa State Univ., Ames, IA (United States); Stockholm Univ., Stockholm (Sweden)
  4. Ames Lab. and Iowa State Univ., Ames, IA (United States); Univ. zu Koln, Koln (Germany)
Publication Date:
Research Org.:
Ames Laboratory (AMES), Ames, IA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1471222
Report Number(s):
IS-J-9752
Journal ID: ISSN 0020-1669
Grant/Contract Number:  
AC02-07CH11358
Resource Type:
Accepted Manuscript
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 57; Journal Issue: 16; 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; 36 MATERIALS SCIENCE

Citation Formats

Rhodehouse, Melissa L., Bell, Thomas, Smetana, Volodymyr, Mudring, Anja -Verena, and Meyer, Gerd H. From the Nonexistent Polar Intermetallic Pt3Pr4 via Pt2–xPr3 to Pt/Sn/Pr Ternaries. United States: N. p., 2018. Web. doi:10.1021/acs.inorgchem.8b01121.
Rhodehouse, Melissa L., Bell, Thomas, Smetana, Volodymyr, Mudring, Anja -Verena, & Meyer, Gerd H. From the Nonexistent Polar Intermetallic Pt3Pr4 via Pt2–xPr3 to Pt/Sn/Pr Ternaries. United States. doi:10.1021/acs.inorgchem.8b01121.
Rhodehouse, Melissa L., Bell, Thomas, Smetana, Volodymyr, Mudring, Anja -Verena, and Meyer, Gerd H. Fri . "From the Nonexistent Polar Intermetallic Pt3Pr4 via Pt2–xPr3 to Pt/Sn/Pr Ternaries". United States. doi:10.1021/acs.inorgchem.8b01121. https://www.osti.gov/servlets/purl/1471222.
@article{osti_1471222,
title = {From the Nonexistent Polar Intermetallic Pt3Pr4 via Pt2–xPr3 to Pt/Sn/Pr Ternaries},
author = {Rhodehouse, Melissa L. and Bell, Thomas and Smetana, Volodymyr and Mudring, Anja -Verena and Meyer, Gerd H.},
abstractNote = {Here the Pt–Pr phase diagram has been explored well, recent work on rare-earth metal cluster halides with endohedral transition metal atoms has provided a new binary intermetallic that is nonexistent in the known phase diagram: The binary Pt3Pr4 (1) crystallizes in a new structure type (mP56, P21/c, a = 12.353(2) Å, b = 7.4837(9) Å, c = 17.279(2) Å, β = 118.003(7)°, Z = 8) with six crystallographically independent Pt as well as eight Pr positions. The subsequent detailed investigation has led to another previously unreported, binary phase with the Ga2Gd3 structure type, Pt2–xPr3 (2, tI80, I4/mcm, a = 11.931(9) Å, c = 14.45(1) Å, Z = 16), that is practically overlapping with the rhombohedral Pt2Pr3 existing in the phase diagram. Application of different tin containing fluxes to reproduce the newly detected phases brought about two almost iso-compositional ternary compounds with Sn, Pt4Sn6Pr2.91 (3), and Pt4Sn6Pr3 (4), as well as Pt12Sn24Pr4.84 (5). 3 is a representative of the Pt4Ge6Ce3 type (oP52, Pnma, a = 7.2863(3) Å, b = 4.4909(2) Å, c = 35.114(2) Å), while 4 represents a new variant of the prolific T4E6R3 family (T = transition metal, E = main group (semi)metal, R = rare-earth metal; Pt4Sn6Pr3: oP52, Pnma, a = 27.623(1) Å, b = 4.5958(2) Å, c = 9.3499(5) Å). Pt12Sn24Pr5–x (5) crystallizes as a variant of the Ni8Sn16Gd3 type (cI82, Im$\bar{3}$, a = 12.274(1) Å, Z = 2). Electronic structure calculations provide hints on the origin of the structural changes (pseudo-polymorphism) for PtxPr3 with x = 1.97 and 2.00, respectively, and reveal that heteroatomic Pt–Pr bonding strongly dominates in both binaries while the addition of the reactive metal tin leads to dominating Pt–Sn bonding interactions in the ternaries; Pt–Pt bonding interactions are strong but represent a minority in the binaries and are not present at all in the ternaries.},
doi = {10.1021/acs.inorgchem.8b01121},
journal = {Inorganic Chemistry},
number = 16,
volume = 57,
place = {United States},
year = {2018},
month = {8}
}

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CSD 1833515: Experimental Crystal Structure Determination: Non-CSD Structure
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CSD 1833516: Experimental Crystal Structure Determination: Non-CSD Structure
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CSD 1833518: Experimental Crystal Structure Determination: Non-CSD Structure
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CSD 1833519: Experimental Crystal Structure Determination: Non-CSD Structure
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Tb 3 Pd 2 , Er 3 Pd 2 and Er 6 Co 5– x : structural variations and bonding in rare-earth-richer binary intermetallics
journal, August 2018

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