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Trigonal prismatic anionic iron (III) complex of a radical o-imino-benzo-semiquinonate derivative: Structural and spectral analysis

Abstract

One new iron(III) complex, [Et3NH][FeIII(L2−•)2] (1) with a substituted o-aminophenol-based ligand is reported. Complex 1 is an anionic complex with a triethylammonium cation in the lattice and contains two O,O,N-coordinated o-iminobenzosemiquinonate(2-) radical anions with Fe(III) centre in high-spin configuration. The crystal structure of 1 was determined by X-ray diffraction to reveal a trigonal prismatic coordination environment whose electronic structure was established by various physical methods including EPR and Mössbauer spectroscopy and variable-temperature (2-300 K) magnetic susceptibility measurements. Electrochemical analysis indicates primarily ligand-centred redox processes. Complex 1, retains the high-spin character of the Fe(III) throughout the temperature range studied (2-290 K) and exhibits, as expected, strong antiferromagnetic coupling operating between two radicals (SR=1/2) and the high-spin Fe(III) centre (SFe=5/2) yielding an St=3/2 as the ground state. Later has been confirmed by means of DFT calculations (M06-2X/6-31+G*) and spin density analysis of the high spin and low spin configurations.

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Publication details

The article was received on 11 Apr 2017, accepted on 01 Jun 2017 and first published on 02 Jun 2017


Article type: Paper
DOI: 10.1039/C7NJ01212H
Citation: New J. Chem., 2017, Accepted Manuscript
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    Trigonal prismatic anionic iron (III) complex of a radical o-imino-benzo-semiquinonate derivative: Structural and spectral analysis

    S. Saha, C. R. Choudhury, C. J. Gomez Garcia, S. Benmansour, E. Garribba, A. Frontera, C. Rizzoli and S. Mitra, New J. Chem., 2017, Accepted Manuscript , DOI: 10.1039/C7NJ01212H

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