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Title: New highly charged iron(III) metal-organic cube stabilized by a bulky amine.
Author: Cruz, Carlos
Vega Carvallo, Andrés Igor
Spodine, Evgenia
Escuer Fité, Albert
Marco, José F.
Menéndez, Nieves
Venegas Yazigi, Diego
Paredes García, Verónica
Keywords: Espectrometria de masses
Espectroscòpia de raigs X
Mass spectrometry
X-ray spectroscopy
Issue Date: 14-Aug-2020
Publisher: American Chemical Society
Abstract: In 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]·10DMF·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 μ-1κ2 N,O:2κ2 N',O‴-IDC3- bridges. Additionally, the magnetic measurements reveal a weak antiferromagnetic coupling in the Fe8 III 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.
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It is part of: ACS Omega , 2020, vol. 5, num. 35, p. 22238-22247
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ISSN: 2470-1343
Appears in Collections:Articles publicats en revistes (Química Inorgànica i Orgànica)

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