Photochemical Synthesis and Characterization of Xenon(VI) Hexafluoridomanganates(IV)

Zoran Mazej, Evgeny Goreshnik, Zvonko Jagličić, Yaroslav Filinchuk, Nikolay Tumanov, Lev G. Akselrud

Research output: Contribution to journalArticle

Abstract

Reactions between XeF2, MnF3 and UV-irradiated elemental F2 in anhydrous HF have yielded [XeF5]2[MnF6] and XeF5MnF5; meanwhile, [XeF5]4[Mn8F36] has been observed as a minor phase upon the crystallization of the product obtained by fluorination of an n(XeF2)/n(MnF3) = 1:3 mixture in the presence of an UV source. The crystal structure of [XeF5]2[MnF6] is isotypic with the known [XeF5]2[PdF6]. Its asymmetric structural unit consists of two crystallographically unique [XeF5]+ cations and a [MnF6]2– anion. The single-crystal structure determination of XeF6·2MnF4 reveals that it is better formulated as [XeF5]4[Mn8F36]. Discrete octameric [Mn8F36]4– anions are built from eight MnF6 octahedra, each sharing three vertices, in the shape of a ring, which is different from the previously known cubic [Ti8F36]4– anion. The main structural feature of the anionic part of the crystal structure of [XeF5][MnF5] (determined from both X-ray single-crystal and synchrotron X-ray powder diffraction data) is infinite zigzag chains of distorted MnF6 octahedra that share cis vertices. [XeF5][MnF5] is paramagnetic in the 296–200 K temperature range, with a Curie constant of C = 1.87 emu K mol–1eff = 3.87 µB) and a Curie–Weiss temperature of θ = –9.3 K. Below 100 K, there is weak antiferromagnetic coupling between the MnIV ions, with a coupling constant of J = –1.3 cm–1. Raman spectra showed that [XeF5]2[MnF6] decomposes at ambient temperature in a He–Ne laser beam (power > 1.7 mW) to [XeF5][MnF5], with further decomposition to MnF3.

LanguageEnglish
Pages2130-2137
Number of pages8
JournalEuropean Journal of Inorganic Chemistry
Volume2017
Issue number14
DOIs
StatePublished - 10 Apr 2017

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Xenon
Anions
Crystal structure
Single crystals
Fluorination
Curie temperature
Crystallization
Synchrotrons
X ray powder diffraction
Laser beams
Cations
Raman scattering
Ions
Decomposition
X rays
Temperature

Keywords

  • Fluorides
  • Magnetic properties
  • Manganese
  • Structure elucidation
  • Xenon hexafluoride

Cite this

Mazej, Z., Goreshnik, E., Jagličić, Z., Filinchuk, Y., Tumanov, N., & Akselrud, L. G. (2017). Photochemical Synthesis and Characterization of Xenon(VI) Hexafluoridomanganates(IV). DOI: 10.1002/ejic.201700054
Mazej, Zoran ; Goreshnik, Evgeny ; Jagličić, Zvonko ; Filinchuk, Yaroslav ; Tumanov, Nikolay ; Akselrud, Lev G./ Photochemical Synthesis and Characterization of Xenon(VI) Hexafluoridomanganates(IV). In: European Journal of Inorganic Chemistry. 2017 ; Vol. 2017, No. 14. pp. 2130-2137
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abstract = "Reactions between XeF2, MnF3 and UV-irradiated elemental F2 in anhydrous HF have yielded [XeF5]2[MnF6] and XeF5MnF5; meanwhile, [XeF5]4[Mn8F36] has been observed as a minor phase upon the crystallization of the product obtained by fluorination of an n(XeF2)/n(MnF3) = 1:3 mixture in the presence of an UV source. The crystal structure of [XeF5]2[MnF6] is isotypic with the known [XeF5]2[PdF6]. Its asymmetric structural unit consists of two crystallographically unique [XeF5]+ cations and a [MnF6]2– anion. The single-crystal structure determination of XeF6·2MnF4 reveals that it is better formulated as [XeF5]4[Mn8F36]. Discrete octameric [Mn8F36]4– anions are built from eight MnF6 octahedra, each sharing three vertices, in the shape of a ring, which is different from the previously known cubic [Ti8F36]4– anion. The main structural feature of the anionic part of the crystal structure of [XeF5][MnF5] (determined from both X-ray single-crystal and synchrotron X-ray powder diffraction data) is infinite zigzag chains of distorted MnF6 octahedra that share cis vertices. [XeF5][MnF5] is paramagnetic in the 296–200 K temperature range, with a Curie constant of C = 1.87 emu K mol–1 (µeff = 3.87 µB) and a Curie–Weiss temperature of θ = –9.3 K. Below 100 K, there is weak antiferromagnetic coupling between the MnIV ions, with a coupling constant of J = –1.3 cm–1. Raman spectra showed that [XeF5]2[MnF6] decomposes at ambient temperature in a He–Ne laser beam (power > 1.7 mW) to [XeF5][MnF5], with further decomposition to MnF3.",
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Mazej, Z, Goreshnik, E, Jagličić, Z, Filinchuk, Y, Tumanov, N & Akselrud, LG 2017, 'Photochemical Synthesis and Characterization of Xenon(VI) Hexafluoridomanganates(IV)' European Journal of Inorganic Chemistry, vol. 2017, no. 14, pp. 2130-2137. DOI: 10.1002/ejic.201700054

Photochemical Synthesis and Characterization of Xenon(VI) Hexafluoridomanganates(IV). / Mazej, Zoran; Goreshnik, Evgeny; Jagličić, Zvonko; Filinchuk, Yaroslav; Tumanov, Nikolay; Akselrud, Lev G.

In: European Journal of Inorganic Chemistry, Vol. 2017, No. 14, 10.04.2017, p. 2130-2137.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Photochemical Synthesis and Characterization of Xenon(VI) Hexafluoridomanganates(IV)

AU - Mazej,Zoran

AU - Goreshnik,Evgeny

AU - Jagličić,Zvonko

AU - Filinchuk,Yaroslav

AU - Tumanov,Nikolay

AU - Akselrud,Lev G.

PY - 2017/4/10

Y1 - 2017/4/10

N2 - Reactions between XeF2, MnF3 and UV-irradiated elemental F2 in anhydrous HF have yielded [XeF5]2[MnF6] and XeF5MnF5; meanwhile, [XeF5]4[Mn8F36] has been observed as a minor phase upon the crystallization of the product obtained by fluorination of an n(XeF2)/n(MnF3) = 1:3 mixture in the presence of an UV source. The crystal structure of [XeF5]2[MnF6] is isotypic with the known [XeF5]2[PdF6]. Its asymmetric structural unit consists of two crystallographically unique [XeF5]+ cations and a [MnF6]2– anion. The single-crystal structure determination of XeF6·2MnF4 reveals that it is better formulated as [XeF5]4[Mn8F36]. Discrete octameric [Mn8F36]4– anions are built from eight MnF6 octahedra, each sharing three vertices, in the shape of a ring, which is different from the previously known cubic [Ti8F36]4– anion. The main structural feature of the anionic part of the crystal structure of [XeF5][MnF5] (determined from both X-ray single-crystal and synchrotron X-ray powder diffraction data) is infinite zigzag chains of distorted MnF6 octahedra that share cis vertices. [XeF5][MnF5] is paramagnetic in the 296–200 K temperature range, with a Curie constant of C = 1.87 emu K mol–1 (µeff = 3.87 µB) and a Curie–Weiss temperature of θ = –9.3 K. Below 100 K, there is weak antiferromagnetic coupling between the MnIV ions, with a coupling constant of J = –1.3 cm–1. Raman spectra showed that [XeF5]2[MnF6] decomposes at ambient temperature in a He–Ne laser beam (power > 1.7 mW) to [XeF5][MnF5], with further decomposition to MnF3.

AB - Reactions between XeF2, MnF3 and UV-irradiated elemental F2 in anhydrous HF have yielded [XeF5]2[MnF6] and XeF5MnF5; meanwhile, [XeF5]4[Mn8F36] has been observed as a minor phase upon the crystallization of the product obtained by fluorination of an n(XeF2)/n(MnF3) = 1:3 mixture in the presence of an UV source. The crystal structure of [XeF5]2[MnF6] is isotypic with the known [XeF5]2[PdF6]. Its asymmetric structural unit consists of two crystallographically unique [XeF5]+ cations and a [MnF6]2– anion. The single-crystal structure determination of XeF6·2MnF4 reveals that it is better formulated as [XeF5]4[Mn8F36]. Discrete octameric [Mn8F36]4– anions are built from eight MnF6 octahedra, each sharing three vertices, in the shape of a ring, which is different from the previously known cubic [Ti8F36]4– anion. The main structural feature of the anionic part of the crystal structure of [XeF5][MnF5] (determined from both X-ray single-crystal and synchrotron X-ray powder diffraction data) is infinite zigzag chains of distorted MnF6 octahedra that share cis vertices. [XeF5][MnF5] is paramagnetic in the 296–200 K temperature range, with a Curie constant of C = 1.87 emu K mol–1 (µeff = 3.87 µB) and a Curie–Weiss temperature of θ = –9.3 K. Below 100 K, there is weak antiferromagnetic coupling between the MnIV ions, with a coupling constant of J = –1.3 cm–1. Raman spectra showed that [XeF5]2[MnF6] decomposes at ambient temperature in a He–Ne laser beam (power > 1.7 mW) to [XeF5][MnF5], with further decomposition to MnF3.

KW - Fluorides

KW - Magnetic properties

KW - Manganese

KW - Structure elucidation

KW - Xenon hexafluoride

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Mazej Z, Goreshnik E, Jagličić Z, Filinchuk Y, Tumanov N, Akselrud LG. Photochemical Synthesis and Characterization of Xenon(VI) Hexafluoridomanganates(IV). European Journal of Inorganic Chemistry. 2017 Apr 10;2017(14):2130-2137. Available from, DOI: 10.1002/ejic.201700054