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Published on: February 5, 2022
Ferromagnetic dinuclear mixed-valence Mn(II)/Mn(III) complexes: building blocks for the higher nuclearity complexes.
Mikko M Hänninen1, Juha Välivaara, Antonio J Mota
1Department of Chemistry, University of Jyväskylä, P.O. Box 35, 40014 Jyväskylä, Finland.
Abstract:
A series of six mixed-valence Mn(II)/Mn(III) dinuclear complexes were synthesized and characterized by X-ray diffraction. The reactivity of the complexes was surveyed, and structures of three additional trinuclear mixed-valence Mn(III)/Mn(II)/Mn(III) species were resolved. The magnetic properties of the complexes were studied in detail both experimentally and theoretically. All dinuclear complexes show ferromagnetic intramolecular interactions, which were justified on the basis of the electronic structures of the Mn(II) and Mn(III) ions. The large Mn(II)-O-Mn(III) bond angle and small distortion of the Mn(II) cation from the ideal square pyramidal geometry were shown to enhance the ferromagnetic interactions since these geometrical conditions seem to favor the orthogonal arrangement of the magnetic orbitals.
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