Metal fluorides with 3D open structures, pyrochlore (pyr) or hexagonal
tungsten bronze (HTB), are promising materials as positive electrodes
for rechargeable batteries or catalysts. Herein, we have developed
a two-step synthesis procedure to obtain new anhydrous mixed-metal-cation
fluorides crystallizing in the pyrochlore structure. The first step
consists of preparing mixed-metal ammonium fluorides (NH4)M2+Fe3+F6 (M = Mn, Fe, Co Ni) using
different synthesis strategies. For M = Mn, three allotropic varieties
of (NH4)Mn2+Fe3+F6 are
obtained; two phases adopt the expected pyrochlore network with either
the cubic Fm3̅m or the orthorhombic Pnma space group, and the third phase exhibits a 3D network
with narrow pseudotriangular cavities. 57Fe Mössbauer
spectrometry indicates that the crystal structures are governed by
the Fe3+/Mn2+ cationic order or disorder. The
second step is a topotactic oxidation of pyr-(NH4)M2+Fe3+F6 under a molecular F2 flow. To better understand the reaction mechanism, the topotactic
oxidation was followed by thermogravimetry, XRD, FTIR, and Mössbauer
spectrometry. The successful synthesis of the first anhydrous pyr-M3+
0.5Fe0.5F3 provides a new
route to prepare anhydrous mixed-metal fluorides pyrochlore with empty
cavities of the open framework.