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A five-coordinate manganese(III) complex of a salen type ligand with a positive axial anisotropy parameter D

Abstract

A new high-spin d4 trigonal-bipyramidal (TBP) manganese(III) complex with a salen type ligand (H2L), namely MnL(NCS)·0.4H2O, has been synthesised and characterised by elemental analysis, ESI mass spectrometry, IR und UV‒vis spectroscopies and spectroelectrochemistry. X-ray diffraction revealed an axial compression of the TBP. Temperature dependent magnetic susceptibility and variable temperature-variable field (VTVH) magnetisation measurements, as well as high-frequency and -field EPR (HFEPR) spectroscopy were used to accurately describe the magnetic properties of this complex, and, in particular, the spin Hamiltonian parameters: g-values and zero-field splitting (ZFS) parameters D and E. The HFEPR spectra allowed extraction of fourth order ZFS parameters. Quantum chemical calculations reproduced well the electronic and geometric structure of this unusual complex, and, in particular, its electronic absorption spectrum along with the spin Hamiltonian parameters.

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Publication details

The article was received on 18 May 2017, accepted on 07 Aug 2017 and first published on 08 Aug 2017


Article type: Paper
DOI: 10.1039/C7DT01809F
Citation: Dalton Trans., 2017, Accepted Manuscript
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    A five-coordinate manganese(III) complex of a salen type ligand with a positive axial anisotropy parameter D

    S. Sova, A. Vlad, M. Cazacu, J. Krzystek, L. Bucinsky, M. Breza, D. Darvasiova, P. Rapta, J. Cano, J. Telser and V. Arion, Dalton Trans., 2017, Accepted Manuscript , DOI: 10.1039/C7DT01809F

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