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Issue 3, 2018
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Hexanuclear iron(III) α-aminophosphonate: synthesis, structure, and magnetic properties of a molecular wheel

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Abstract

A new hexanuclear molecular iron phosphonate complex, [Fe6(HAIPA)12(OH)6nH2O (1·nH2O) (H2AIPA = NH2(CH3)2CP(O)(OH)2, (2-aminopropan-2-yl)phosphonic acid), was synthesized from Fe2+ and Fe3+ salts in water by interaction with the ligand salts. Addition of corresponding amounts of sodium or tetramethylammonium salts of H2AIPA to the solution of iron precursors led to the formation of large bright-green crystals of complex 1. Isolated products were studied by spectroscopic and analytical methods – IR, Mössbauer spectroscopy, TG/DSC, ICP-OES, and CHN analysis. A novel {Fe6} hexanuclear molecular structure of 1 was confirmed by single crystal X-ray diffraction analysis. An octahedral coordination environment of iron cations is formed by phosphonate and hydroxo oxygens. Twelve phosphonate groups and six –OH groups act as bridging ligands and bind six Fe octahedra. Because of protonation of the amino group, the phosphonate anions coordinate in the zwitterionic form as HAIPA (NH3+(CH3)2CPO32−). The iron cations are present in the form of high-spin Fe3+, which was confirmed by the bond valence sum (BVS) calculations and the 57Fe Mössbauer spectra. The magnetic measurements show antiferromagnetic coupling between the iron centers with decreasing temperature.

Graphical abstract: Hexanuclear iron(iii) α-aminophosphonate: synthesis, structure, and magnetic properties of a molecular wheel

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The article was received on 20 Sep 2017, accepted on 18 Dec 2017 and first published on 12 Jan 2018


Article type: Paper
DOI: 10.1039/C7NJ03606J
Citation: New J. Chem., 2018,42, 1931-1938
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    Hexanuclear iron(III) α-aminophosphonate: synthesis, structure, and magnetic properties of a molecular wheel

    I. Doroshenko, M. Babiak, A. Buchholz, J. Tucek, W. Plass and J. Pinkas, New J. Chem., 2018, 42, 1931
    DOI: 10.1039/C7NJ03606J

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