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New Highly Charged Iron(III) Metal-Organic Cube Stabilized by a Bulky Amine

AuthorsCruz, C. CSIC ORCID; Vega Carvallo, A.I.; Spodine, E.; Escuer, A.; Marco, J.F. CSIC ORCID ; Menéndez, Nieves; Venegas-Yazigi, D.; Paredes-García, V.
Issue Date14-Aug-2020
PublisherAmerican Chemical Society
CitationACS Omega 5: 22238-22247 (2020)
AbstractIn this work, we report a new octanuclear cluster based on FeIII and the ligand 1H-imidazole-4,5-dicarboxylic acid, [Et3NH]12[Fe8(IDC)12]middot10DMF 13H2O (1), with a metal core containing eight FeIII connected by only one type of organic ligand. A peak at 573 m/z in the mass spectra of the compound suggests the adduct species {[Fe8(IDC)12]+8H}4-. By X-ray photoelectron spectroscopy, the oxidation state of the iron cation was confirmed to be 3+, also identifying the presence of a quaternary nitrogen species, which act as a countercation of the anionic metal core [Fe8(IDC)12]12-. Mössbauer spectra recorded at different temperatures show an isomer shift and quadrupole splitting parameters that confirm the existence of only FeIII-HS in the structure of 1. X-ray analysis reveals that compound 1 crystallizes in the orthorhombic system space group Ibam, confirming a molecular cluster structure with an almost regular cube as geometry, with the FeIII atoms located at the corners of the cube and connected by κ2N,O:2κ2N,Oâ IDC3- bridges. Additionally, the magnetic measurements reveal a weak antiferromagnetic coupling in the Fe8III coordination cluster (J =-3.8 cm-1). To the best of our knowledge, 1 is the first member of the family of cubes assembled with 1H-imidazole-4,5-dicarboxylic acid and FeIII cation, exhibiting high pH stability over a broad pH range, making it an ideal candidate for the design of supramolecular structures and metal-organic frameworks.
Description10 pags., 5 figs., 2 tabs.
Publisher version (URL)http://dx.doi.org/10.1021/acsomega.0c02420
Identifiersdoi: 10.1021/acsomega.0c02420
issn: 2470-1343
Appears in Collections:(IQFR) Artículos
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