Li<sub>4</sub><i>Ln</i>[PS<sub>4</sub>]<sub>2</sub>Cl: Chloride-Containing Lithium Thiophosphates with Lanthanoid Participation (<i>Ln</i> = Pr, Nd and Sm)
The synthesis and structural analysis of three new chloride-containing lithium thiophosphates(V) Li<sub>4</sub><i>Ln</i>[PS<sub>4</sub>]<sub>2</sub>Cl with trivalent lanthanoids (<i>Ln</i> = Pr, Nd and Sm) are presented and discussed. Singl...
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| Format: | Article |
| Language: | English |
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MDPI AG
2023-09-01
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| Series: | Crystals |
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| Online Access: | https://www.mdpi.com/2073-4352/13/10/1408 |
| _version_ | 1797574202387070976 |
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| author | Pia L. Lange Sebastian Bette Sabine Strobel Robert E. Dinnebier Thomas Schleid |
| author_facet | Pia L. Lange Sebastian Bette Sabine Strobel Robert E. Dinnebier Thomas Schleid |
| author_sort | Pia L. Lange |
| collection | DOAJ |
| description | The synthesis and structural analysis of three new chloride-containing lithium thiophosphates(V) Li<sub>4</sub><i>Ln</i>[PS<sub>4</sub>]<sub>2</sub>Cl with trivalent lanthanoids (<i>Ln</i> = Pr, Nd and Sm) are presented and discussed. Single crystals of Li<sub>4</sub>Sm[PS<sub>4</sub>]<sub>2</sub>Cl were obtained and used for crystal structure determination by applying X-ray diffraction. The other compounds were found to crystallize isotypically in the monoclinic space group <i>C</i>2/<i>c</i>. Thus, Li<sub>4</sub>Sm[PS<sub>4</sub>]<sub>2</sub>Cl (<i>a</i> = 2089.31(12) pm, <i>b</i> = 1579.69(9) pm, <i>c</i> = 1309.04(8) pm, <i>β</i> = 109.978(3)°, <i>Z</i> = 12) was used as a representative model to further describe the crystal structure in detail since Li<sub>4</sub>Pr[PS<sub>4</sub>]<sub>2</sub>Cl and Li<sub>4</sub>Nd[PS<sub>4</sub>]<sub>2</sub>Cl were confirmed to be isotypic using powder X-ray diffraction measurements (PXRD). In all cases, a trigonal structure in the space group <i>R</i><inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><mover><mn>3</mn><mo>¯</mo></mover></mrow></semantics></math></inline-formula> (e.g., <i>a</i> = 1579.67(9) pm, <i>c</i> = 2818.36(16) pm, <i>c/a</i> = 1.784, <i>Z</i> = 18, for Li<sub>4</sub>Sm[PS<sub>4</sub>]<sub>2</sub>Cl) displaying almost identical building units worked initially misleadingly. The structure refinement of Li<sub>4</sub>Sm[PS<sub>4</sub>]<sub>2</sub>Cl revealed bicapped trigonal prisms of sulfur atoms coordinating the two crystallographically distinct (Sm1)<sup>3+</sup> and (Sm2)<sup>3+</sup> cations, which are further coordinated by four anionic [PS<sub>4</sub>]<sup>3−</sup> tetrahedra. The compounds also contain chloride anions residing within channel-like pores made of [PS<sub>4</sub>]<sup>3−</sup> units. Eight different sites for Li<sup>+</sup> cations were identified with various coordination environments (<i>C.N.</i> = 4–6) with respect to chlorine and sulfur. EDXS measurements supported the stoichiometric formula of Li<sub>4</sub><i>Ln</i>[PS<sub>4</sub>]<sub>2</sub>Cl, and diffuse reflectance spectroscopy revealed optical band gaps of 2.69 eV, 3.52 eV, and 3.49 eV for Li<sub>4</sub>Sm[PS<sub>4</sub>]<sub>2</sub>Cl, Li<sub>4</sub>Nd[PS<sub>4</sub>]<sub>2</sub>Cl, and Li<sub>4</sub>Pr[PS<sub>4</sub>]<sub>2</sub>Cl, respectively. The activation energy for Li<sup>+</sup>-cation mobility in Li<sub>4</sub>Sm[PS<sub>4</sub>]<sub>2</sub>Cl was calculated as <i>E</i><sub>a</sub>(Li<sup>+</sup>) = 0.88 eV using BVEL, which indicates potential as a Li<sup>+</sup>-cation conductor. |
| first_indexed | 2024-03-10T21:19:37Z |
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| id | doaj.art-5436b6a48db948c3880f9b641b9a27af |
| institution | Directory Open Access Journal |
| issn | 2073-4352 |
| language | English |
| last_indexed | 2024-03-10T21:19:37Z |
| publishDate | 2023-09-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Crystals |
| spelling | doaj.art-5436b6a48db948c3880f9b641b9a27af2023-11-19T16:08:48ZengMDPI AGCrystals2073-43522023-09-011310140810.3390/cryst13101408Li<sub>4</sub><i>Ln</i>[PS<sub>4</sub>]<sub>2</sub>Cl: Chloride-Containing Lithium Thiophosphates with Lanthanoid Participation (<i>Ln</i> = Pr, Nd and Sm)Pia L. Lange0Sebastian Bette1Sabine Strobel2Robert E. Dinnebier3Thomas Schleid4Institute for Inorganic Chemistry, University of Stuttgart, Pfaffenwaldring 55, 70569 Stuttgart, GermanyMax Planck Institute for Solid State Research, Heisenbergstraße 1, 70569 Stuttgart, GermanyInstitute for Inorganic Chemistry, University of Stuttgart, Pfaffenwaldring 55, 70569 Stuttgart, GermanyMax Planck Institute for Solid State Research, Heisenbergstraße 1, 70569 Stuttgart, GermanyInstitute for Inorganic Chemistry, University of Stuttgart, Pfaffenwaldring 55, 70569 Stuttgart, GermanyThe synthesis and structural analysis of three new chloride-containing lithium thiophosphates(V) Li<sub>4</sub><i>Ln</i>[PS<sub>4</sub>]<sub>2</sub>Cl with trivalent lanthanoids (<i>Ln</i> = Pr, Nd and Sm) are presented and discussed. Single crystals of Li<sub>4</sub>Sm[PS<sub>4</sub>]<sub>2</sub>Cl were obtained and used for crystal structure determination by applying X-ray diffraction. The other compounds were found to crystallize isotypically in the monoclinic space group <i>C</i>2/<i>c</i>. Thus, Li<sub>4</sub>Sm[PS<sub>4</sub>]<sub>2</sub>Cl (<i>a</i> = 2089.31(12) pm, <i>b</i> = 1579.69(9) pm, <i>c</i> = 1309.04(8) pm, <i>β</i> = 109.978(3)°, <i>Z</i> = 12) was used as a representative model to further describe the crystal structure in detail since Li<sub>4</sub>Pr[PS<sub>4</sub>]<sub>2</sub>Cl and Li<sub>4</sub>Nd[PS<sub>4</sub>]<sub>2</sub>Cl were confirmed to be isotypic using powder X-ray diffraction measurements (PXRD). In all cases, a trigonal structure in the space group <i>R</i><inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><mover><mn>3</mn><mo>¯</mo></mover></mrow></semantics></math></inline-formula> (e.g., <i>a</i> = 1579.67(9) pm, <i>c</i> = 2818.36(16) pm, <i>c/a</i> = 1.784, <i>Z</i> = 18, for Li<sub>4</sub>Sm[PS<sub>4</sub>]<sub>2</sub>Cl) displaying almost identical building units worked initially misleadingly. The structure refinement of Li<sub>4</sub>Sm[PS<sub>4</sub>]<sub>2</sub>Cl revealed bicapped trigonal prisms of sulfur atoms coordinating the two crystallographically distinct (Sm1)<sup>3+</sup> and (Sm2)<sup>3+</sup> cations, which are further coordinated by four anionic [PS<sub>4</sub>]<sup>3−</sup> tetrahedra. The compounds also contain chloride anions residing within channel-like pores made of [PS<sub>4</sub>]<sup>3−</sup> units. Eight different sites for Li<sup>+</sup> cations were identified with various coordination environments (<i>C.N.</i> = 4–6) with respect to chlorine and sulfur. EDXS measurements supported the stoichiometric formula of Li<sub>4</sub><i>Ln</i>[PS<sub>4</sub>]<sub>2</sub>Cl, and diffuse reflectance spectroscopy revealed optical band gaps of 2.69 eV, 3.52 eV, and 3.49 eV for Li<sub>4</sub>Sm[PS<sub>4</sub>]<sub>2</sub>Cl, Li<sub>4</sub>Nd[PS<sub>4</sub>]<sub>2</sub>Cl, and Li<sub>4</sub>Pr[PS<sub>4</sub>]<sub>2</sub>Cl, respectively. The activation energy for Li<sup>+</sup>-cation mobility in Li<sub>4</sub>Sm[PS<sub>4</sub>]<sub>2</sub>Cl was calculated as <i>E</i><sub>a</sub>(Li<sup>+</sup>) = 0.88 eV using BVEL, which indicates potential as a Li<sup>+</sup>-cation conductor.https://www.mdpi.com/2073-4352/13/10/1408crystal structurelanthanoidsthiophosphateslithiumchlorides |
| spellingShingle | Pia L. Lange Sebastian Bette Sabine Strobel Robert E. Dinnebier Thomas Schleid Li<sub>4</sub><i>Ln</i>[PS<sub>4</sub>]<sub>2</sub>Cl: Chloride-Containing Lithium Thiophosphates with Lanthanoid Participation (<i>Ln</i> = Pr, Nd and Sm) Crystals crystal structure lanthanoids thiophosphates lithium chlorides |
| title | Li<sub>4</sub><i>Ln</i>[PS<sub>4</sub>]<sub>2</sub>Cl: Chloride-Containing Lithium Thiophosphates with Lanthanoid Participation (<i>Ln</i> = Pr, Nd and Sm) |
| title_full | Li<sub>4</sub><i>Ln</i>[PS<sub>4</sub>]<sub>2</sub>Cl: Chloride-Containing Lithium Thiophosphates with Lanthanoid Participation (<i>Ln</i> = Pr, Nd and Sm) |
| title_fullStr | Li<sub>4</sub><i>Ln</i>[PS<sub>4</sub>]<sub>2</sub>Cl: Chloride-Containing Lithium Thiophosphates with Lanthanoid Participation (<i>Ln</i> = Pr, Nd and Sm) |
| title_full_unstemmed | Li<sub>4</sub><i>Ln</i>[PS<sub>4</sub>]<sub>2</sub>Cl: Chloride-Containing Lithium Thiophosphates with Lanthanoid Participation (<i>Ln</i> = Pr, Nd and Sm) |
| title_short | Li<sub>4</sub><i>Ln</i>[PS<sub>4</sub>]<sub>2</sub>Cl: Chloride-Containing Lithium Thiophosphates with Lanthanoid Participation (<i>Ln</i> = Pr, Nd and Sm) |
| title_sort | li sub 4 sub i ln i ps sub 4 sub sub 2 sub cl chloride containing lithium thiophosphates with lanthanoid participation i ln i pr nd and sm |
| topic | crystal structure lanthanoids thiophosphates lithium chlorides |
| url | https://www.mdpi.com/2073-4352/13/10/1408 |
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