An [Feᴵᴵᴵ₃₄] molecular metal oxide

Dearle, A. E. et al. (2019) An [Feᴵᴵᴵ₃₄] molecular metal oxide. Angewandte Chemie (International Edition), 58(47), pp. 16903-16906. (doi: 10.1002/anie.201911003) (PMID:31535459) (PMCID:PMC7186828)

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The dissolution of anhydrous iron bromide in a mixture of pyridine and acetonitrile, in the presence of an organic amine, results in the formation of an [Fe₃₄] metal oxide molecule, structurally characterised by alternate layers of tetrahedral and octahedral Feᴵᴵᴵ ions connected by oxide and hydroxide ions. The outer shell of the complex is capped by a combination of pyridine molecules and bromide ions. Magnetic data, measured at temperatures as low as 0.4 K and fields up to 35 T, reveal competing antiferromagnetic exchange interactions; DFT calculations showing that the magnitudes of the coupling constants are highly dependent on both the Fe‐O‐Fe angles and Fe−O distances. The simplicity of the synthetic methodology, and the structural similarity between [Fe₃₄], bulk iron oxides, previous Feᴵᴵᴵ–oxo cages, and polyoxometalates (POMs), hints that much larger molecular Feᴵᴵᴵ oxides can be made.

Item Type:Articles
Additional Information:E.K.B. thanks the EPSRC for funding (grants EP/N01331X/1 and EP/P025986/1). G.R. thanks UGC‐UKIERI grant number 184‐1/2018(lC) and SERB (CRG/2018/000430). S.D. thanks the UGC for an SRF fellowship. M.E. thanks MICINN (RTI2018‐094909‐J‐I00). J.S. thanks the Deutsche Forschungsgemeinschaft DFG (314331397 (SCHN 615/23‐1).
Glasgow Author(s) Enlighten ID:Lee, Mr Eddy and Cronin, Professor Lee
Authors: Dearle, A. E., Cutler, D. J., Fraser, H. W. L., Sanz, S., Lee, E., Dey, S., Diaz-Ortega, I. F., Nichol, G. S., Nojiri, H., Evangelisti, M., Rajaraman, G., Schnack, J., Cronin, L., and Brechin, E. K.
College/School:College of Science and Engineering > School of Chemistry
Journal Name:Angewandte Chemie (International Edition)
ISSN (Online):1521-3773
Published Online:19 September 2019
Copyright Holders:Copyright © 2019 The Authors
First Published:First published in Angewandte Chemie (International Edition) 58(47): 16903-16906
Publisher Policy:Reproduced under a Creative Commons License

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