[Cr^III₈Ni^II₆]n+ heterometallic coordination cubes

O'Connor, Helen M., Sanz, Sergio, Scott, Aaron J., Pitak, Mateusz, Klooster, Wim, Coles, Simon J., Chilton, Nicholas F., McInnes, Eric J.L., Lusby, Paul J., Weihe, Høgni, Piligkos, Stergios and Brechin, Euan K. (2021) [Cr^III₈Ni^II₆]n+ heterometallic coordination cubes. Molecules, 26 (3), [757]. (doi:10.3390/molecules26030757).

Abstract

Three new heterometallic [Cr^III₈Ni^II₆] coordination cubes of formulae  [Cr^III₈Ni^II₆L₂₄(H₂O)₁₂](NO₃)₁₂ (1), [Cr^III₈Ni^II₆L₂₄(MeCN)₇(H₂O)₅](ClO₄)₁₂ (2), and [Cr^III₈Ni^II₆L₂₄Cl₁₂] (3) (where HL = 1-(4-pyridyl)butane-1,3-dione), were synthesised using the paramagnetic metalloligand [Cr^IIIL₃] 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 Cr^III and Ni^II ions, with JCr-Ni = + 0.045 cm−1. EPR spectra are consistent with weak exchange, being dominated by the zero-field splitting of the Cr^III 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 [M^III₈M^II₆] cubes, where MIII = Cr, Fe and MII = Cu, Co, Mn, Pd.

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Contributors

Author: Mateusz Pitak

Author: Simon J. Coles

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