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

As a consequence of the static Jahn-Teller effect of the E-5 ground state of Mn-III 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 K-3[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 Mn-III Jahn-Teller systems. Owing to the internal electric field of C-i symmetry dominated by the next-neighbour K+ ions acting on the Mn-III sites, both sites, the pseudo-rhombic (site 1) and the pseudo-tetragonally elongated (site 2) [MnF6](3-) anions are present in K-3[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.

Automated summary

The synthesis of the compound K-3[MnF6] was reported using a high-temperature approach and crystallized by a high-pressure/high-temperature route. The compound contains two structural motifs of [MnF6]3- anions with significantly different nature.