Modular [(Fe8M6II)-M-III](&ITn&IT+)(M-II = Pd, Co, Ni, Cu) Coordination Cages

Sergio Sanz, Helen M. O'Connor, Priyanka Comar, Amgalanbaatar Baldansuren, Mateusz B. Pitak, Simon J. Coles, Hogni Weihe, Nicholas F. Chilton, Eric J. L. McInnes, Paul J. Lusby, Stergios Piligkos, Euan K. Brechin

Research output: Contribution to journalArticlepeer-review

Abstract

The reaction of the simple metalloligand [(FeL3)-L-III] [HL = 1-(4-pyridyl)butane-1,3-dione] with a variety of different M-II salts results in the formation of a family of heterometallic cages of formulae [Fe(8)(III)pd(6)(II)L(24)]Cl-12 (1), [(Fe8Cu6L24)-Cu-III-L-II(H2O)(4) Br-4]Br-8 (2), [(Fe8Cu6L24)-Cu-III-L-II(H2O)(10)] (NO3)(12) (3), [(Fe8N6L24)-N-III-L-II(SCN)(11)Cl] (4), and [(FeIII8Cu6L24)-L-II(SCN)(10)(H2(O))(2)]Cl-2 (5). The metallic skeleton of each cage describes a cube in which the Fe-III ions occupy the eight vertices and the M-II 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 nudear physics as statistical spectroscopy, which exploit the moments of the Hamiltonian to calculate relevant thermodynamic properties, determine J(Fe-Cu) = 0.10 cm(-1) for 3 and J(Fe-Ni) = 0.025 cm(-1) for 4. Q-band electron paramagnetic resonance spectra of 1 reveal a significantly wider spectral width in comparison to [FeL3], indicating that the magnitude of the Fe-III zero-field splitting is larger in the heterometallic cage than in the monomer.

Original languageEnglish
Pages (from-to)3500-3506
Number of pages7
JournalInorganic Chemistry
Volume57
Issue number7
Early online date11 Jan 2018
DOIs
Publication statusPublished - 2 Apr 2018

Keywords

  • MAGNETIC-PROPERTIES
  • CONSTRUCTION
  • COMPLEXES
  • CLUSTERS

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