Department of Chemistry, University of Jyväskylä, P.O. Box 35, 40014 Jyväskylä, Finland.
Inorg Chem. 2013 Feb 18;52(4):2228-41. doi: 10.1021/ic302731z. Epub 2013 Jan 30.
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.
一系列六个混合价态 Mn(II)/Mn(III)双核配合物被合成并通过 X 射线衍射进行了表征。研究了配合物的反应性，并解析了另外三个三核混合价态 Mn(III)/Mn(II)/Mn(III)物种的结构。详细研究了配合物的磁性，既通过实验也通过理论。所有双核配合物都显示出铁磁分子内相互作用，这是基于 Mn(II)和 Mn(III)离子的电子结构来证明的。大的 Mn(II)-O-Mn(III)键角和 Mn(II)阳离子从理想的四方锥形几何结构的小变形被表明增强了铁磁相互作用，因为这些几何条件似乎有利于磁轨道的正交排列。
