Oxidation of europium with ammonium perfluorocarboxylates in liquid ammonia: pathways to europium(ii) carboxylates and hexanuclear europium(iii) fluoridocarboxylate complexes

Abstract

The novel coordination polymer [Eu(O₂CCF₃)₂(dmf)₂]_∞ (1) (dmf = N,N-dimethylformamide) containing europium(II) and the two new compounds (NH₄)₂[Eu₆F₈(O₂CCF₃)₁₂(CF₃COOH)₆] (2) and (NH₄)₂[Eu₆F₈(O₂CC₂F₅)₁₂(C₂F₅COOH)₆]·8C₂F₅COOH (3), both based on hexanuclear europiate(III) complexes, were synthesized from precursors with a Eu²⁺ : Eu³⁺ ratio >1, obtained by reaction of europium metal with ammonium perfluorocarboxylates in liquid ammonia. In the crystal structure of 1 the europium(II) ions are bridged by carboxylate groups and N,N-dimethylformamide to form polymeric chains with Eu²⁺⋯Eu²⁺ distances of 408.39(13)–410.49(13) pm. The compound crystallizes in the triclinic space group P (Z = 2). To the best of our knowledge, this is the first example of a (solvated) perfluorocarboxylate containing a lanthanoid in a subvalent oxidation state. In the crystal structures of 2 and 3 the europium(III) ions are bridged by fluoride ions and carboxylate groups to form hexanuclear complex anions with an octahedral arrangement of the cations. The Eu³⁺⋯Eu³⁺ distances are in the range of 398.27(15)–400.93(15) pm in 2 and 395.37(4)–399.78(5) pm in 3, respectively. Both compounds crystallize in the monoclinic space group type P2₁/n (Z = 4) and are the first examples of octahedro-hexanuclear europium carboxylates for which fluoride is reported as a bridging ligand. In all compounds the oxidation state of europium was monitored via¹⁵¹Eu Mössbauer and photoluminescene spectroscopy.