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Slow magnetic relaxation in Fe(II) m-terphenyl complexes.

Andrew J Valentine1, Ana M Geer2, Toby J Blundell3

  • 1School of Chemistry, University Park, University of Nottingham, Nottingham, NG7 2RD, UK. laurence.taylor@nottingham.ac.uk.

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We synthesized five two-coordinate iron complexes that function as single-molecule magnets. Electron-donating substituents on the ligands enhanced magnetic relaxation, showing potential for versatile ligand design.

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Area of Science:

  • Coordination Chemistry
  • Magnetism
  • Materials Science

Background:

  • Two-coordinate transition metal complexes offer highly axial coordination environments, ideal for single-molecule magnets (SMMs).
  • These complexes exhibit significant magnetic anisotropy, a key property for SMMs.

Purpose of the Study:

  • To investigate the magnetic properties of a series of two-coordinate iron(II) m-terphenyl complexes.
  • To explore how functionalization of the para-substituent influences the magnetic behavior and relaxation rates of these complexes.

Main Methods:

  • Synthesis of five structurally related two-coordinate Fe(II) m-terphenyl complexes with varying para-substituents (R).
  • Magnetic characterization to determine field-induced single-molecule magnet behavior.
  • Analysis of magnetic relaxation rates using direct and Raman mechanisms.
  • Ab initio calculations to predict crystal field and zero-field splitting parameters.

Main Results:

  • All five synthesized complexes exhibit field-induced single-molecule magnet behavior.
  • Magnetic relaxation rates were successfully modeled by direct and Raman mechanisms.
  • Electron-donating para-substituents were found to significantly slow the magnetic relaxation rate.
  • Calculations predicted large crystal field splitting (>850 cm-1) and sizable zero-field splitting parameters (ca. -60 cm-1).

Conclusions:

  • The study demonstrates that modifying the para-substituent on m-terphenyl ligands can tune the magnetic function of two-coordinate iron complexes.
  • m-terphenyl ligands show promise as versatile building blocks for creating effective single-molecule magnets due to their ability to induce highly axial crystal fields.