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From the Nonexistent Polar Intermetallic Pt3Pr4 via Pt2-xPr3 to Pt/Sn/Pr Ternaries
Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK). Iowa State University, United States.ORCID iD: 0000-0003-0763-1457
Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK). Iowa State University, United States.ORCID iD: 0000-0002-2800-1684
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Number of Authors: 52018 (English)In: Inorganic Chemistry, ISSN 0020-1669, E-ISSN 1520-510X, Vol. 57, no 16, p. 9949-9961Article in journal (Refereed) Published
Abstract [en]

Although 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) angstrom, b = 7.4837(9) angstrom, c = 17.279(2) angstrom, beta = 118.003(7)degrees, 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) A, c = 14.45(1) angstrom, 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 temary compounds with Sn, Pt4Sn6Pr2.91 (3), and Pt4.Sn6Pr3 (4), as well as Pt12Sn24Pr4.84 (5). 3 is a representative of the Pt4Ge6Ce3 type (oP52, Pnma, a = 7.2863(3) A, b = 4.4909(2) angstrom, c = 35.114(2) angstrom), while 4 represents a new variant of the prolific T4E6R3 family (T = transition metal, E = main group (semOrnetal, R = rare-earth metal; Pt4Sn6Pr3: oP52, Pnma, a = 27.623(1) angstrom, b = 4.5958(2) A, c = 9.3499(5) A). Pt(12)sn(24)Prs_x (5) crystallizes as a variant of the Ni8Sn16Gd3 type (cI82, /m(-3), a = 12.274(1) A, 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.

Place, publisher, year, edition, pages
2018. Vol. 57, no 16, p. 9949-9961
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Chemical Sciences
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URN: urn:nbn:se:su:diva-160086DOI: 10.1021/acs.inorgchem.8b01121ISI: 000442489100042PubMedID: 30073839OAI: oai:DiVA.org:su-160086DiVA, id: diva2:1251112
Available from: 2018-09-26 Created: 2018-09-26 Last updated: 2022-02-26Bibliographically approved

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Smetana, VolodyrnyrMudring, Anja-Verena

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