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

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

Résultats de recherche: Contribution à un journal/une revueArticle

Résumé

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.

langueAnglais
Pages2130-2137
Nombre de pages8
journalEuropean Journal of Inorganic Chemistry
Volume2017
Numéro14
Les DOIs
étatPublié - 10 avr. 2017

Empreinte digitale

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

mots-clés

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    Mazej, Z., Goreshnik, E., Jagličić, Z., Filinchuk, Y., Tumanov, N., & Akselrud, L. G. (2017). Photochemical Synthesis and Characterization of Xenon(VI) Hexafluoridomanganates(IV). European Journal of Inorganic Chemistry, 2017(14), 2130-2137. 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). Dans: European Journal of Inorganic Chemistry. 2017 ; Vol 2017, Numéro 14. p. 2130-2137
    @article{9812599352d9418185d09f54a9c2009c,
    title = "Photochemical Synthesis and Characterization of Xenon(VI) Hexafluoridomanganates(IV)",
    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.",
    keywords = "Fluorides, Magnetic properties, Manganese, Structure elucidation, Xenon hexafluoride",
    author = "Zoran Mazej and Evgeny Goreshnik and Zvonko Jagličić and Yaroslav Filinchuk and Nikolay Tumanov and Akselrud, {Lev G.}",
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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, Numéro 14, p. 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.

    Dans: European Journal of Inorganic Chemistry, Vol 2017, Numéro 14, 10.04.2017, p. 2130-2137.

    Résultats de recherche: Contribution à un journal/une revueArticle

    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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    DO - 10.1002/ejic.201700054

    M3 - Article

    VL - 2017

    SP - 2130

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    JO - European Journal of Inorganic Chemistry

    T2 - European Journal of Inorganic Chemistry

    JF - European Journal of Inorganic Chemistry

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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 avr. 10;2017(14):2130-2137. Disponible �, DOI: 10.1002/ejic.201700054