Issue 12, 2022

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[1 with combining macron] (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.

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

Supplementary files

Article information

Article type
Paper
Submitted
14 Dez 2021
Accepted
25 Feb 2022
First published
01 Mär 2022
This article is Open Access
Creative Commons BY-NC license

Dalton Trans., 2022,51, 4814-4828

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

F. Morsbach, S. Klenner, R. Pöttgen and W. Frank, Dalton Trans., 2022, 51, 4814 DOI: 10.1039/D1DT04204A

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