Ionothermal Synthesis, Structures, and Magnetism of Three New Open Framework Iron Halide-Phosphates

A set of different open framework iron phosphates have been synthesized ionothermally using a task-specific ionic liquid, 1-butyl-4-methylpyridinium hexafluorophosphate, that acts in the synthesis as the reaction medium and mineralizer: (NH₄)₂Fe₂(HPO₄)(PO₄)Cl₂F (1) and K₂Fe₂(HPO₄)(PO₄)Cl₂F (2) exhibit similar composition and closely related structural features. Both structures consist of {Fe₂(HPO₄)(PO₄)Cl₂F}^2- macroanions and charge balancing ammonium or potassium cations. Their open framework structure contains layers and chains of corner-linked {Fe(1)O₂Cl₄} and {Fe(2)F₂O₄} octahedra, respectively, interconnected by PO₄ tetrahedra forming 10-ring channels. KFe(PO₃F)F₂ (3) is built up by {Fe[(PO₃F)_4/3F_2/2]}{Fe(PO₃F)_2/3F_2/2F₂} layers separated by K⁺ cations. Chains of alternating {FeF₂O₄} and {FeO₂F₄} octahedra, which are linear for 1 but undulated for 2, are linked to each other via corner-sharing {PO₃F} tetrahedra with the fluorine pointing into the interlayer space. The compounds were characterized by means of single crystal and powder X-ray diffraction, infrared spectroscopy, and magnetic measurements. 1 reveals a strong ground state spin anisotropy with a spin 5/2 state and a magnetic moment of 5.3 μ_B/Fe³⁺. Specific heat and magnetic data unveil three magnetic transitions at 95, 50, and 3.6 K. Compound 2 has a very similar crystal structure as compared to 1 but exhibits a different magnetic behavior: a slightly lower magnetic moment of 4.7 μ_B/Fe³⁺ and a magnetic transition to a canted antiferromagnetic state below 90 K. Compound 3 exhibits typical paramagnetic behavior close to room-temperature (5.71 μ_B/Fe³⁺). There are no clear indications for a phase transition down to 2 K despite strong antiferromagnetic spin-spin interactions; only a magnetic anomaly appears at 50 K in the zero-field cooled data.