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Ferromagnetically coupled dinuclear MII complexes based on a boratriazine ligand framework.

Jamie M Savard1, Gabriel Brunet, Anandi Srinivasan

  • 1Department of Chemistry and Biomolecular Sciences, University of Ottawa, Ottawa, Ontario K1N 6N5, Canada. jbrusso@uottawa.ca.

Dalton Transactions (Cambridge, England : 2003)
|October 4, 2018
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Summary

New iron(II) and cobalt(II) complexes were synthesized using a novel boratriazine ligand. These complexes exhibit ferromagnetic interactions due to a unique double azido bridging motif, paving the way for advanced magnetic materials.

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Area of Science:

  • Coordination Chemistry
  • Inorganic Materials Science
  • Magnetochemistry

Background:

  • Boratriazine ligands combine properties of bodipy and terpy units.
  • Azido ligands are known to mediate magnetic exchange interactions in metal complexes.
  • Dinuclear metal complexes are foundational for developing molecular magnetism.

Purpose of the Study:

  • To synthesize novel dinuclear iron(II) and cobalt(II) complexes using a tailored boratriazine ligand.
  • To investigate the magnetic properties and bridging modes within these new complexes.
  • To establish a new precedent for ferromagnetic coupling in dinuclear iron(II) systems.

Main Methods:

  • Synthesis of dinuclear iron(II) and cobalt(II) complexes, denoted as 1 and 2, respectively.
  • Crystallographic characterization to determine molecular structure and bridging motifs.
  • Magnetic susceptibility measurements to quantify magnetic exchange interactions (J) and zero-field splitting (D).

Main Results:

  • Complexes [Fe2II(μ1,1-N3)2(Py2F2BTA)2(N3)2] (1) and [Co2II(μ1,1-N3)2(Py2F2BTA)2(N3)2] (2) were successfully synthesized.
  • Both complexes feature a double end-on azido bridging ligand, facilitating ferromagnetic coupling.
  • Complex 1 is the first reported dinuclear FeII complex with this bridging mode, showing J = 5.7(9) cm-1 and D = -6.0(4) cm-1. The cobalt analogue (2) exhibits J = 7.1(9) cm-1 and D = 17.3(9) cm-1.

Conclusions:

  • The novel boratriazine ligand enables the formation of dinuclear metal complexes with specific magnetic properties.
  • The double end-on azido bridge is an effective motif for inducing ferromagnetic interactions in both iron(II) and cobalt(II) systems.
  • These findings contribute to the design of new molecular magnetic materials with tunable properties.