A thorough study of structural and magnetic properties was performed on a series of trinuclear and dinuclear Mn(III)/Fe(III) complexes consisting of [M(L4)(Solv)](+) and [Fe(CN)5(NO)](2-) moieties (M = Fe(III) or Mn(III), Solv = H2O or CH3OH, L4 = tetradentate salen-type ligands), in which dominant magnetic exchange is mediated by O(S)-H···O(Ph) hydrogen bonds in [M(L4)(Solv)](+)···[M(L4)(Solv)](+) supramolecular dimers. As deduced from magnetic analysis involving the determination of zero-field splitting (ZFS) parameters for Mn(III) and Fe(III) ions, as well as from comprehensive DFT calculations and modelling, it may be concluded that the strength of the magnetic exchange is correlated with the number of hydrogen bonds and with the O(Ph)···O(S) distance between the phenolic oxygen atom of the salen-type ligand (O(Ph)) and the oxygen atom of the solvent molecule coordinated to the adjacent metal atom (O(S)).

Regional Centre of Advanced Technologies and Materials and Department of Inorganic Chemistry Faculty of Science Palacký University 17 listopadu 12 771 46 Olomouc Czech Republic

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Pentacoordinate and Hexacoordinate Mn(III) Complexes of Tetradentate Schiff-Base Ligands Containing Tetracyanidoplatinate(II) Bridges and Revealing Uniaxial Magnetic Anisotropy