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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Abstract
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). |
| Status: | Published |
| Refereed: | Yes |
| 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) |
| Publisher: | Wiley |
| ISSN: | 1433-7851 |
| 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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