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Modular [FeIII8MII6]n+ (MII = Pd, Co, Ni, Cu) coordination cages

DOI: 10.1021/acs.inorgchem.7b02674 DOI Help

Authors: Sergio Sanz (University of Edinburgh) , Helen M. O'Connor (University of Edinburgh) , Priyanka Comar (University of Edinburgh) , Amgalanbaatar Baldansuren (The University of Manchester) , Mateusz B. Pitak (University of Southampton) , Simon J. Coles (University of Southampton) , Høgni Weihe (University of Copenhagen) , Nicholas F. Chilton (The University of Manchester) , Eric J. L. Mcinnes (The University of Manchester) , Paul J. Lusby (University of Edinburgh) , Stergios Piligkos (University of Copenhagen) , Euan K. Brechin (University of Edinburgh)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Inorganic Chemistry

State: Published (Approved)
Published: January 2018
Diamond Proposal Number(s): 11238

Abstract: 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 significantly wider spectral width in comparison to [FeL3], indicating that the magnitude of the FeIII zero-field splitting is larger in the heterometallic cage than in the monomer.

Journal Keywords: Palladium; Ions; Magnetic properties; Electron paramagnetic resonance spectroscopy; Quantum mechanics

Subject Areas: Chemistry

Instruments: I19-Small Molecule Single Crystal Diffraction

Added On: 15/01/2018 09:13

Discipline Tags:

Molecular Complexes Chemistry Inorganic Chemistry

Technical Tags:

Diffraction Single Crystal X-ray Diffraction (SXRD)