Cyanide-bridged WVMnIII bimetallic chains composed of a blocked W hexacyanide precursor: Geometry-related magnetic couplings and magnetostructural correlation

Jin Wuk Lee, Kwang Soo Lim, Dae Won Ryu, Eui Kwan Koh, Sung Won Yoon, Byoung Jin Suh, Chang Seop Hong

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Five one-dimensional bimetallic WVMnIII complexes 1-5, consisting of [W(CN)6(bpy)]- anions and [Mn(Schiff base)]+ cations, were prepared. The central coordination geometry around each W atom is determined as a distorted dodecahedron (DD) for 1 and 2, and a distorted square antiprism (SAPR) for 3-5. Magnetic analyses demonstrate that compounds 1, 4, and 5 exhibit antiferromagnetic interactions between magnetic centers, which are different from the ferromagnetic couplings in 2 and 3. For the distorted DD geometry, the Mn-Nax (ax = axial) bond length increases when moving from 1 to 2, with the Mn-Nax-Cax angle remaining constant. The elongation of the bond length is responsible for the reduction in orbital overlap and consequent ferromagnetic coupling in 2. In comparison, for 3-5 with the distorted SAPR geometry, given that the Mn-N ax bond lengths are similar across all the samples, the increase in the Mn-Nax-Cax angles accounts for the enhanced magnetic strength. Notably, a correlation between structure and magnetic exchange coupling is established for the first time in WVMnIII bimetallic systems based on the [W(CN)6(bpy)]- precursor.

Original languageEnglish
Pages (from-to)8677-8684
Number of pages8
JournalInorganic Chemistry
Issue number15
Publication statusPublished - 2013 Aug 5


ASJC Scopus subject areas

  • Inorganic Chemistry
  • Physical and Theoretical Chemistry

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