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Modular [FeIII8MII6]n+ (MII = Pd, Co, Ni, Cu) Coordination Cages

The reaction of the simple metalloligand [FeIIIL3] [HL = 1-(4-pyridyl)butane-1,3-dione] with a variety of different MII salts results in the formation of a family of heterometallic cages of formulae [FeIII8PdII6L24]Cl12 (1), [FeIII8CuII6L24(H2O)4Br4]Br8 (2), [FeIII8CuII6L24(H2O)10](NO3)12 (3), [FeIII8NiII6L24(SCN)11Cl] (4), and [FeIII8CoII6L24(SCN)10(H2O)2]Cl2 (5). The metallic skeleton of each cage describes a cube in which the FeIII ions occupy the eight vertices and the MII ions lie at the center of the six faces. Direct-current magnetic susceptibility and magnetization measurements on 3–5 reveal the presence of weak antiferromagnetic exchange between the metal ions in all three cases. Computational techniques known in theoretical nuclear physics as statistical spectroscopy, which exploit the moments of the Hamiltonian to calculate relevant thermodynamic properties, determine JFe–Cu = 0.10 cm–1 for 3 and JFe–Ni = 0.025 cm–1 for 4. Q-band electron paramagnetic resonance spectra of 1 reveal a significant...

Authors:   Sergio Sanz; Helen M. O’Connor; Priyanka Comar; Amgalanbaatar Baldansuren; Mateusz B. Pitak; Simon J. Coles; Høgni Weihe; Nicholas F. Chilton; Eric J. L. McInnes; Paul J. Lusby; Stergios Piligkos; Euan K. Brechin
Journal:   Inorganic Chemistry
Year:   2018
DOI:   10.1021/acs.inorgchem.7b02674
Publication date:   11-Jan-2018
Facts, background information, dossiers
  • nuclear physics
  • metal ions
  • magnetization
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