Dinuclear manganese(III) complexes with bioinspired coordination and variable linkers showing weak exchange effects: a synthetic, structural, spectroscopic and computation study

Sergiu Shova; Angelica Vlad; Maria Cazacu; J. Krzystek; Andrew Ozarowski; Michal Malček; Lukas Bucinsky; Peter Rapta; Joan Cano; Joshua Telser; Vladimir B. Arion

doi:10.1039/C8DT04596H

Dinuclear manganese(iii) complexes with bioinspired coordination and variable linkers showing weak exchange effects: a synthetic, structural, spectroscopic and computation study†

Sergiu Shova,^a Angelica Vlad,^a Maria Cazacu,

^a J. Krzystek,

^b Andrew Ozarowski,

^b Michal Malček,^c Lukas Bucinsky,^c Peter Rapta,^c Joan Cano,

^d Joshua Telser

*^e and Vladimir B. Arion

*^f

Author affiliations

* Corresponding authors

^a Inorganic Polymers Department, “Petru Poni” Institute of Macromolecular Chemistry, Aleea Gr. Ghica Voda 41 A, Iasi 700487, Romania

^b National High Magnetic Field Laboratory, Florida State University, Tallahassee, Florida 32310, USA

^c Institute of Physical Chemistry and Chemical Physics, Slovak University of Technology in Bratislava, Radlinského 9, 81237 Bratislava, Slovak Republic

^d Institut de Ciència Molecular, Universitat de València, Catedrático José Beltrán Martínez 2, 46980 Paterna, Spain

^e Department of Biological, Physical and Health Sciences, Roosevelt University, 430 S. Michigan Avenue, Chicago, Illinois 60605, USA
E-mail: jtelser@roosevelt.edu

^f Institute of Inorganic Chemistry of the University of Vienna, Währinger Strasse 42, A1090 Vienna, Austria
E-mail: vladimir.arion@univie.ac.at

Abstract

Three dimanganese(III) complexes have been synthesised and fully characterised by standard spectroscopic methods and spectroelectrochemistry. Each Mn^III ion is chelated by a salen type ligand (H₂L), but there is variation in the bridging group: LMn(OOCCH [double bond, length as m-dash] CHCOO)MnL, LMn(OOCC₆H₄COO)MnL, and LMn(OOCC₆H₄C₆H₄COO)MnL. X-ray diffraction revealed an axial compression of each six-coordinate high-spin d⁴ Mn^III ion, which is a Jahn–Teller-active ion. 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 the complexes, not only the single-ion spin Hamiltonian parameters: g-values and zero-field splitting (ZFS) parameters D and E, but also the exchange interaction constant J between the two ions, which has been seldom determined for a di-Mn^III complex, particularly when there is more than a single bridging atom. Quantum chemical calculations reproduced well the electronic and geometric structure of these unusual complexes, and, in particular, their electronic absorption spectra along with the spin Hamiltonian and exchange parameters.

This article is part of the themed collection: Bioinspired reactivity and coordination chemistry

Dalton Transactions

Dinuclear manganese(iii) complexes with bioinspired coordination and variable linkers showing weak exchange effects: a synthetic, structural, spectroscopic and computation study†

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Dinuclear manganese(III) complexes with bioinspired coordination and variable linkers showing weak exchange effects: a synthetic, structural, spectroscopic and computation study

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