Manganese(III) fluorophosphate frameworks.

ABSTRACT

Nine new manganese(III) fluorophosphates have been synthesised hydrothermally in a fluoride-rich medium, through the use of MnF(3), HPF(6) and monovalent metal fluorides as reactants. Products have been structurally characterised using single crystal X-ray diffraction. Reaction in fluoride-rich conditions produces chain, layer and three dimensional framework structures containing new and unusual structural features based on the linking of PO(3)F, PO(2)(OH,F)(2) and Mn(O(6-n),F(n)) octahedra, with n averaging 2.8 over the family of compounds. The Mn(III), d(4), oxidation state is stabilised under these reaction conditions and products frequently show Jahn-Teller distorted Mn(O,F)(6) units with axially elongated Mn-O or, less commonly, Mn-F distances. Structures exhibiting inter-layer spaces and channels frequently have these lined by terminal fluoride anions of the PO(3)F, PO(2)(OH,F)(2) and Mn(O,F)(6) octahedra.