[CrIII8NiII6]n+ Heterometallic Coordination Cubes

Helen M. O'Connor, Sergio Sanz, Aaron J. Scott, Mateusz B. Pitak, Wim T. Klooster, Simon J. Coles, Nicholas F. Chilton, Eric J.L. McInnes, Paul J. Lusby, Høgni Weihe, Stergios Piligkos, Euan K. Brechin

Research output: Contribution to journalArticlepeer-review

Abstract

Three new heterometallic [CrIII8NiII6] coordination cubes of formulae [CrIII8NiII6L24(H2O)12](NO3)12 (1), [CrIII8NiII6L24(MeCN)7(H2O)5](ClO4)12 (2), and [CrIII8NiII6L24Cl12] (3) (where HL = 1-(4-pyridyl)butane-1,3-dione), were synthesised using the paramagnetic metalloligand [CrIIIL3] and the corresponding NiII salt. The magnetic skeleton of each capsule describes a face-centred cube in which the eight CrIII and six NiII ions occupy the eight vertices and six faces of the structure, respectively. Direct current magnetic susceptibility measurements on (1) reveal weak ferromagnetic interactions between the CrIII and NiII ions, with JCr-Ni = + 0.045 cm-1. EPR spectra are consistent with weak exchange, being dominated by the zero-field splitting of the CrIII ions. Excluding wheel-like structures, examples of large heterometallic clusters containing both CrIII and NiII ions are rather rare, and we demonstrate that the use of metalloligands with predictable bonding modes allows for a modular approach to building families of related polymetallic complexes. Compounds (1)-(3) join the previously published, structurally related family of [MIII8MII6] cubes, where MIII = Cr, Fe and MII = Cu, Co, Mn, Pd.
Original languageEnglish
Article number757
Number of pages9
JournalMolecules (Basel, Switzerland)
Volume26
Issue number3
Early online date2 Feb 2021
DOIs
Publication statusE-pub ahead of print - 2 Feb 2021

Keywords

  • EPR spectroscopy
  • heterometallic clusters
  • magnetometry
  • molecular magnetism
  • supramolecular chemistry

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