Cyano-bridged pentanuclear and honeycomblike MIIICuII (M = Fe, Cr) bimetallic assemblies: Structural variations modulated by side groups of macrocyclic ligands and magnetic properties

Jeong Hak Lim, Jung Hee Yoon, Sang Yup Choi, Dae Won Ryu, Eui Kwan Koh, Chang Seop Hong

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Abstract

Three two-dimensional (2D) layered M(III)-Cu(II) (M = Fe, Cr) bimetallic complexes and a discrete cluster were prepared using [M(CN)6] 3- and respective Cu macrocycles with methyl (1, 3) or ethyl (2, 4) side groups. The crystal structures can be described as aesthetic honeycomb-like M2Cu3 neutral sheets (1, 3, 4) and a pentanuclear Fe 2Cu3 entity (2) with an isolated Cu(L2)2+ moiety. The steric hindrance induced by the pendant groups renders the internal parameters of the Cu-Nax (where the "ax" subscript denotes axial) length and Cu-Nax-Cax angle to become elongated and acute. The magnetic data disclose that ferromagnetic couplings are transmitted between M(III) and Cu(II) ions through the CN links. For 4, particularly, there is a magnetically defined chain (Jc) composed of dimers (J d) and trimers (Jt), based on the structural considerations. The intramolecular magnetic coupling constants are Jd = 3.73 cm-1 and Jt = 4.08 cm-1, while the Jc value corresponds to 0.17 cm-1. From a magnetostructural point of view, it is reasoned that the Cu-Nax bond length is probably a determining factor of the strength of magnetic couplings in 4.

Original languageEnglish
Pages (from-to)1749-1757
Number of pages9
JournalInorganic Chemistry
Volume50
Issue number5
DOIs
Publication statusPublished - 2011 Mar 7

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ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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