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[CrIII8NiII6]n+ heterometallic coordination cubes

DOI: 10.3390/molecules26030757 DOI Help

Authors: Helen M. O’connor (The University of Edinburgh) , Sergio Sanz (The University of Edinburgh) , Aaron J. Scott (The University of Edinburgh) , Mateusz B. Pitak (University of Southampton) , Wim T. Klooster (University of Southampton) , Simon J. Coles (University of Southampton) , Nicholas F. Chilton (The University of Manchester) , Eric J. L. Mcinnes (The University of Manchester) , Paul J. Lusby (The University of Edinburgh) , Høgni Weihe (University of Copenhagen) , Stergios Piligkos (University of Copenhagen) , Euan K. Brechin (The University of Edinburgh)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Molecules , VOL 26

State: Published (Approved)
Published: February 2021
Diamond Proposal Number(s): 11238

Open Access Open Access

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.

Journal Keywords: molecular magnetism; supramolecular chemistry; heterometallic clusters; magnetometry; EPR spectroscopy

Subject Areas: Chemistry


Instruments: I19-Small Molecule Single Crystal Diffraction

Documents:
molecules-26-00757.pdf

Discipline Tags:

Molecular Complexes Physical Chemistry Chemistry

Technical Tags:

Diffraction Single Crystal X-ray Diffraction (SXRD)