Synthesis of New Perovskite-Type Oxyfluoride, PbMnO2F

Katsumata, Tetsuhiro; Nakashima, Mamoru; Inaguma, Yoshiyuki; Tsurui, Takao

doi:10.1246/bcsj.20110295

Cited by 17 publications

(8 citation statements)

References 15 publications

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“…Numerous AB O 2 F perovskites ( A = K, Sr, Pb, etc., B = Ti, Mn, Fe, etc.) have been reported to date. − In contrast, Tl I Tl III OF 2 is the only example of AB OF 2 . AgFeOF 2 represents the first transition-metal oxyfluoride with F/O = 2.…”

Section: Resultsmentioning

confidence: 97%

“…These features are partly related to the more ionic character of the F – anion, compared with the oxide anion. The perovskite structure affords the formation of several oxyfluorides with transition metals at the B -site, as found in KTiO 2 F, A NbO 2 F ( A = Na, K), Pb M O 2 F ( M = Sc, Mn), and A FeO 2 F ( A = Sr, − Pb, − Ba , ), and they are accessible via conventional solid-state reactions (e.g., A NbO 2 F), high-pressure reactions (e.g., KTiO 2 F and Pb M O 2 F), and topochemical fluorination reactions (e.g., A FeO 2 F).…”

Section: Introductionmentioning

confidence: 94%

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AgFeOF₂: A Fluorine-Rich Perovskite Oxyfluoride

et al. 2018

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We synthesized a silver iron oxyfluoride AgFeOF by using a high-pressure reaction. Synchrotron X-ray and neutron diffraction, X-ray absorption, and Fe Mössbauer spectroscopy indicate that AgFeOF crystallizes in the ideal perovskite structure with iron in a trivalent state, although electron microscopy revealed weak super-reflections. A possible partial ordering in the FeOF octahedron is inferred from Mössbauer spectroscopy. The synthesis of the fluorine-rich sample offers an opportunity to study a composition-property relation in AFeOF ( n = 0, 1, and 2). AgFeOF exhibits a G-type antiferromagnetic ordering below T ≈ 480 K, which is much lower than the n = 0 and 1 cases, suggesting a weaker superexchange interaction between Fe moments via F 2p orbitals (vs O 2p orbitals).

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Section: Resultsmentioning

confidence: 97%

Section: Introductionmentioning

confidence: 94%

AgFeOF₂: A Fluorine-Rich Perovskite Oxyfluoride

et al. 2018

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“…Another useful approach toward mixed-anion compounds is the high-pressure method, by which two new perovskite manganese compounds, i.e., PbMnO 2 F and MnTaO 2 N, have been obtained. Recently, our research group has successfully extended the RP-type layered oxyhalide series using this technique.…”

Section: Introductionmentioning

confidence: 99%

High-Pressure Synthesis, Crystal Structure, and Magnetic Properties of Sr₂MnO₃F: A New Member of Layered Perovskite Oxyfluorides

Tsujimoto²,

Matsushita³

et al. 2016

Inorg. Chem.

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We have successfully synthesized Sr2MnO3F, a new layered perovskite oxyfluoride with a n = 1 Ruddlesden-Popper-type structure using a high-pressure, high-temperature method. Structural refinements against synchrotron X-ray diffraction data collected from manganese oxyfluoride demonstrated that it crystallizes in a tetragonal cell with the space group I4/mmm, in which the Mn cation is located at the octahedral center position. This is in stark contrast to the related oxyhalides that have square-pyramidal coordination such as Sr2MO3X (M = Fe, Co, Ni; X = F, Cl) and Sr2MnO3Cl. There was no evidence of O/F site order, but close inspection of the anion environment centered at the Mn cation on the basis of bond-valence-sum calculation suggested preferential occupation of the apical sites by the F ion with one oxide ion in a random manner. Magnetic susceptibility and heat capacity measurements revealed an antiferromagnetic ordering at 133 K (=TN), which is much higher than that of the chloride analogue with corrugated MnO2 planes (TN = 80 K).

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“…Thus, F − prefers more open site compared to O 2− , leading to O/F anion order. However, in spite of a simple perovskite, partial anion order is reported for PbFeO 2 F, accompanied with a tetragonal distortion [24,25]. The anisotropic instability observed in this and similar systems (PbTiO 3 [26], Pb(Zr x Ti 1−x ) O 3 [27], and BiFeO 3 [28]), has been attributed to the existence of a the 6s 2 lone pair.…”

Section: Introductionmentioning

confidence: 64%

O/F anion order in Pb$_2$Ti$_4$O$_9$F$_2$ stabilized by the 6$s^2$ lone pair electrons of Pb$^{2+}$

Oka,

Ichibha,

Kato

et al. 2021

Preprint

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Understanding the mechanisms of anionic ordering in mixed anion compounds is a crucial factor for designing their structural and functional properties. Some oxyfluorides are known to exhibit the F − ordering. The ordering is accompanied by a tetragonal distortion, which is believed to be originated by the 6s 2 lone pairs of Bi and Pb. To elucidate the role played by the lone pair, we studied isostructural Bi 2 Ti 4 O 11 and Pb 2 Ti 4 O 9 F 2 with a combination of synchrotron X-ray diffraction techniques and ab initio calculations. Bi 2 Ti 4 O 11 undergoes antiferroelectric-paraelectric transitions from C2/c to C2/m. Meanwhile, Pb 2 Ti 4 O 9 F 2 does not, because F − selectively occupies the closest anion site to Bi/Pb and reduces the distortion. The question on why a particular site is selectively occupied by F − in Pb 2 Ti 4 O 9 F 2 becomes important to understand the role of 6s 2 lone pair electrons for stabilizing the anion order. Our DFT ab initio calculations reproduced the same anionic arrangement in terms of the total energy. However, this energy gain cannot be fully explained by the electrostatic (Madelung) potential alone, being an exception of the Pauling's second rule. We explain the reason focusing on the steric effects of 6s lone pairs. This manuscript has been authored by UT-Battelle, LLC, under Contract No. DE-AC05-00OR22725 with the US Department of Energy (DOE). The US Government retains and the publisher, by accepting the article for publication, acknowledges that the United States Government retains a nonexclusive, paid-up, irrevocable, worldwide license to publish or reproduce the published form of this manuscript, or allow others to do so, for US Government purposes. Ichibha provided a large part of the calculation results. Ichibha and Fernando wrote the paper coworking with the other authors. DOE will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan (http://energy.gov/downloads/doe-public-access-plan).

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Synthesis of New Perovskite-Type Oxyfluoride, PbMnO2F

Cited by 17 publications

References 15 publications

AgFeOF₂: A Fluorine-Rich Perovskite Oxyfluoride

AgFeOF₂: A Fluorine-Rich Perovskite Oxyfluoride

High-Pressure Synthesis, Crystal Structure, and Magnetic Properties of Sr₂MnO₃F: A New Member of Layered Perovskite Oxyfluorides

O/F anion order in Pb$_2$Ti$_4$O$_9$F$_2$ stabilized by the 6$s^2$ lone pair electrons of Pb$^{2+}$

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Synthesis of New Perovskite-Type Oxyfluoride, PbMnO2F

Cited by 17 publications

References 15 publications

AgFeOF2: A Fluorine-Rich Perovskite Oxyfluoride

AgFeOF2: A Fluorine-Rich Perovskite Oxyfluoride

High-Pressure Synthesis, Crystal Structure, and Magnetic Properties of Sr2MnO3F: A New Member of Layered Perovskite Oxyfluorides

O/F anion order in Pb$_2$Ti$_4$O$_9$F$_2$ stabilized by the 6$s^2$ lone pair electrons of Pb$^{2+}$

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Resources

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AgFeOF₂: A Fluorine-Rich Perovskite Oxyfluoride

AgFeOF₂: A Fluorine-Rich Perovskite Oxyfluoride

High-Pressure Synthesis, Crystal Structure, and Magnetic Properties of Sr₂MnO₃F: A New Member of Layered Perovskite Oxyfluorides