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

Sergiu Shova; Angelica Vlad; Maria Cazacu; J Krzystek; Lukas Bucinsky; Martin Breza; Denisa Darvasiová; Peter Rapta; Joan Cano; Joshua Telser; Vladimir B Arion

doi:10.1039/c7dt01809f

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

Dalton Trans. 2017 Sep 12;46(35):11817-11829. doi: 10.1039/c7dt01809f.

Authors

Sergiu Shova¹, Angelica Vlad, Maria Cazacu, J Krzystek, Lukas Bucinsky, Martin Breza, Denisa Darvasiová, Peter Rapta, Joan Cano, Joshua Telser, Vladimir B Arion

Affiliation

¹ Inorganic Polymers Department, "Petru Poni" Institute of Macromolecular Chemistry, Aleea Gr. Ghica Voda 41 A, Iasi 700487, Romania.

PMID: 28848942
DOI: 10.1039/c7dt01809f

Abstract

A new high-spin d⁴ roughly 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 and UV-vis spectroscopy, and spectroelectrochemistry. X-ray diffraction analysis revealed an axial compression of the approximate 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, determine the spin Hamiltonian parameters: g-values and the zero-field splitting (ZFS) parameters D and E. The HFEPR spectra allowed the extraction of fourth order ZFS parameters. Quantum chemical calculations reproduced well the electronic and geometric structures of this unusual complex and, in particular, its electronic absorption spectrum along with the spin Hamiltonian parameters.