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Materials like iron, nickel, and cobalt consist of magnetic domains, within which the magnetic dipoles are arranged parallel to each other. The magnetic dipoles are rigidly aligned in the same direction within a domain by quantum mechanical coupling among the atoms. This coupling is so strong that even thermal agitation at room temperature cannot break it. The result is that each domain has a net dipole moment. However, some materials have weaker coupling, and are ferromagnetic at lower...
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In most main group element compounds, the valence electrons of the isolated atoms combine to form chemical bonds that satisfy the octet rule. For instance, the four valence electrons of carbon overlap with electrons from four hydrogen atoms to form CH4. The one valence electron leaves sodium and adds to the seven valence electrons of chlorine to form the ionic formula unit NaCl (Figure 1a). Transition metals do not normally bond in this fashion. They primarily form coordinate covalent bonds, a...
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A simple methodology for constructing ferromagnetically coupled Cr(iii) compounds.

Hector W L Fraser1, Lucy Smythe, Sourav Dey

  • 1EaStCHEM School of Chemistry, The University of Edinburgh, David Brewster Road, Edinburgh, EH9 3FJ Scotland, UK. E.Brechin@ed.ac.uk.

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Synthesized chromium(iii) dimers with carboxylate ligands exhibit ferromagnetic interactions. Removing the carboxylate bridge in a related compound leads to antiferromagnetic exchange, explained by DFT calculations.

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Area of Science:

  • Inorganic Chemistry
  • Materials Science
  • Magnetochemistry

Background:

  • Chromium(iii) dimers are of interest for their magnetic properties.
  • Ligand design plays a crucial role in tuning magnetic exchange interactions.

Purpose of the Study:

  • To synthesize and characterize a series of chromium(iii) dimers.
  • To investigate the influence of carboxylate ligands on magnetic coupling.
  • To elucidate the mechanism of magnetic exchange interactions.

Main Methods:

  • Synthesis of chromium(iii) dimer compounds.
  • Magneto-structural characterization using direct current (DC) magnetic susceptibility measurements.
  • Density Functional Theory (DFT) calculations.

Main Results:

  • A family of chromium(iii) dimers with general formula [Cr2(R1-deaH)2(O2CR2)Cl2]Cl was synthesized.
  • Ferromagnetic (FM) exchange interactions were observed in carboxylate-bridged dimers (+0.37 < J < +8.02 cm-1).
  • Antiferromagnetic (AFM) exchange was observed in a dialkoxide-bridged analogue lacking a carboxylate bridge.

Conclusions:

  • The presence of a bridging carboxylate ligand promotes ferromagnetic exchange in chromium(iii) dimers.
  • Orbital counter-complementarity is identified as the mechanism for ferromagnetic exchange upon carboxylate bridge introduction.
  • Ligand modification offers a route to control magnetic behavior in dinuclear chromium complexes.