A Site-Ordered Quadruple Perovskites, RMn<sub>3</sub>Ni<sub>2</sub>Mn<sub>2</sub>O<sub>12</sub> with R = Bi, Ce, and Ho, with Different Degrees of B Site Ordering
A site-ordered quadruple perovskites, AA′<sub>3</sub>B<sub>4</sub>O<sub>12</sub>, can have 3<i>d</i> transition metals at A′ and B sites, and show complex magnetic interactions and behavior. Additional complexity appears when B site-ordered arrangement...
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2025-04-01
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| author | Alexei A. Belik |
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| description | A site-ordered quadruple perovskites, AA′<sub>3</sub>B<sub>4</sub>O<sub>12</sub>, can have 3<i>d</i> transition metals at A′ and B sites, and show complex magnetic interactions and behavior. Additional complexity appears when B site-ordered arrangements are realized in AA′<sub>3</sub>B<sub>2</sub>B′<sub>2</sub>O<sub>12</sub>. In this work, A site-ordered quadruple perovskites, RMn<sub>3</sub>Ni<sub>2</sub>Mn<sub>2</sub>O<sub>12</sub> with R = Bi, Ce, and Ho, were prepared by a high-pressure, high-temperature method at about 6 GPa and about 1500 K. The R = Bi and Ce samples were found to crystallize in space group <i>Im</i>-3 with a disordered distribution of Ni<sup>2+</sup> and Mn<sup>4+</sup> cations in one B site. On the other hand, the R = Ho sample crystallized in space group <i>Pn</i>-3 and showed partial ordering of Ni<sup>2+</sup> and Mn<sup>4+</sup> cations between two B sites. The structural data (and bond valence sums) suggest that cerium has the oxidation state +3, which is unusual for such perovskites. Magnetic properties were investigated by magnetic susceptibility and specific heat measurements, which showed the presence of one magnetic transition near 36 K for R = Bi; there was evidence for the presence of two magnetic transitions near 27 K and 33 K for R = Ce, and near 10 K and 36 K for R = Ho. Curie–Weiss parameters were estimated for all samples from high-temperature magnetic measurements up to 750 K. The total effective magnetic moment for R = Ce also suggests the presence of Ce<sup>3+</sup>. A magnetic field of 90 kOe had the largest effect on the specific heat of the R = Ho sample, and almost no effects on the specific heat of the R = Bi sample. |
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| publishDate | 2025-04-01 |
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| spelling | doaj-art-2882f909fb03413aa5c9f7864d04b2e42025-08-20T02:18:04ZengMDPI AGMolecules1420-30492025-04-01308174910.3390/molecules30081749A Site-Ordered Quadruple Perovskites, RMn<sub>3</sub>Ni<sub>2</sub>Mn<sub>2</sub>O<sub>12</sub> with R = Bi, Ce, and Ho, with Different Degrees of B Site OrderingAlexei A. Belik0Research Center for Materials Nanoarchitectonics (MANA), National Institute for Materials Science (NIMS), Namiki 1-1, Tsukuba 305-0044, Ibaraki, JapanA site-ordered quadruple perovskites, AA′<sub>3</sub>B<sub>4</sub>O<sub>12</sub>, can have 3<i>d</i> transition metals at A′ and B sites, and show complex magnetic interactions and behavior. Additional complexity appears when B site-ordered arrangements are realized in AA′<sub>3</sub>B<sub>2</sub>B′<sub>2</sub>O<sub>12</sub>. In this work, A site-ordered quadruple perovskites, RMn<sub>3</sub>Ni<sub>2</sub>Mn<sub>2</sub>O<sub>12</sub> with R = Bi, Ce, and Ho, were prepared by a high-pressure, high-temperature method at about 6 GPa and about 1500 K. The R = Bi and Ce samples were found to crystallize in space group <i>Im</i>-3 with a disordered distribution of Ni<sup>2+</sup> and Mn<sup>4+</sup> cations in one B site. On the other hand, the R = Ho sample crystallized in space group <i>Pn</i>-3 and showed partial ordering of Ni<sup>2+</sup> and Mn<sup>4+</sup> cations between two B sites. The structural data (and bond valence sums) suggest that cerium has the oxidation state +3, which is unusual for such perovskites. Magnetic properties were investigated by magnetic susceptibility and specific heat measurements, which showed the presence of one magnetic transition near 36 K for R = Bi; there was evidence for the presence of two magnetic transitions near 27 K and 33 K for R = Ce, and near 10 K and 36 K for R = Ho. Curie–Weiss parameters were estimated for all samples from high-temperature magnetic measurements up to 750 K. The total effective magnetic moment for R = Ce also suggests the presence of Ce<sup>3+</sup>. A magnetic field of 90 kOe had the largest effect on the specific heat of the R = Ho sample, and almost no effects on the specific heat of the R = Bi sample.https://www.mdpi.com/1420-3049/30/8/1749A site-ordered quadruple perovskitesB site double orderingcrystal structuresstructural disordermagnetic properties |
| spellingShingle | Alexei A. Belik A Site-Ordered Quadruple Perovskites, RMn<sub>3</sub>Ni<sub>2</sub>Mn<sub>2</sub>O<sub>12</sub> with R = Bi, Ce, and Ho, with Different Degrees of B Site Ordering Molecules A site-ordered quadruple perovskites B site double ordering crystal structures structural disorder magnetic properties |
| title | A Site-Ordered Quadruple Perovskites, RMn<sub>3</sub>Ni<sub>2</sub>Mn<sub>2</sub>O<sub>12</sub> with R = Bi, Ce, and Ho, with Different Degrees of B Site Ordering |
| title_full | A Site-Ordered Quadruple Perovskites, RMn<sub>3</sub>Ni<sub>2</sub>Mn<sub>2</sub>O<sub>12</sub> with R = Bi, Ce, and Ho, with Different Degrees of B Site Ordering |
| title_fullStr | A Site-Ordered Quadruple Perovskites, RMn<sub>3</sub>Ni<sub>2</sub>Mn<sub>2</sub>O<sub>12</sub> with R = Bi, Ce, and Ho, with Different Degrees of B Site Ordering |
| title_full_unstemmed | A Site-Ordered Quadruple Perovskites, RMn<sub>3</sub>Ni<sub>2</sub>Mn<sub>2</sub>O<sub>12</sub> with R = Bi, Ce, and Ho, with Different Degrees of B Site Ordering |
| title_short | A Site-Ordered Quadruple Perovskites, RMn<sub>3</sub>Ni<sub>2</sub>Mn<sub>2</sub>O<sub>12</sub> with R = Bi, Ce, and Ho, with Different Degrees of B Site Ordering |
| title_sort | site ordered quadruple perovskites rmn sub 3 sub ni sub 2 sub mn sub 2 sub o sub 12 sub with r bi ce and ho with different degrees of b site ordering |
| topic | A site-ordered quadruple perovskites B site double ordering crystal structures structural disorder magnetic properties |
| url | https://www.mdpi.com/1420-3049/30/8/1749 |
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