Coexistence of Two Different Distorted Octahedral [MnF6]3− Sites in K3[MnF6]: Manifestation in Spectroscopy and Magnetism

Christiane Stoll, Mihail Atanasov*, Jascha Bandemehr, Frank Neese*, Clemens Pietzonka, Florian Kraus, Antti J. Karttunen, Markus Seibald, Gunter Heymann, Hubert Huppertz*

*Corresponding author for this work

Research output: Contribution to journalArticleScientificpeer-review

3 Citations (Scopus)
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As a consequence of the static Jahn-Teller effect of the 5E ground state of MnIII in cubic structures with octahedral parent geometries, their octahedral coordination spheres become distorted. In the case of six fluorido ligands, [MnF6]3− anions with two longer and four shorter Mn−F bonds making elongated octahedra are usually observed. Herein, we report the synthesis of the compound K3[MnF6] through a high-temperature approach and its crystallization by a high-pressure/high-temperature route. The main structural motifs are two quasi-isolated, octahedron-like [MnF6]3− anions of quite different nature compared to that met in ideal octahedral MnIII Jahn-Teller systems. Owing to the internal electric field of Ci symmetry dominated by the next-neighbour K+ ions acting on the MnIII sites, both sites, the pseudo-rhombic (site 1) and the pseudo-tetragonally elongated (site 2) [MnF6]3− anions are present in K3[MnF6]. The compound was characterized by single-crystal and powder X-ray diffraction, and magnetometry as well as by FTIR, Raman, and ligand field spectroscopy. A theoretical interpretation of the electronic structure and molecular geometry of the two Mn sites in the lattice is given by using a vibronic coupling model with parameters adjusted from multireference ab-initio cluster calculations.

Original languageEnglish
Pages (from-to)9801-9813
Number of pages13
JournalChemistry - A European Journal
Issue number38
Early online date28 May 2021
Publication statusPublished - 7 Jul 2021
MoE publication typeA1 Journal article-refereed


  • ab initio calculations
  • fluorides
  • single-crystal determination
  • solid-state reactions


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