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Color in Coordination Complexes
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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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Field-Induced Co(II) Single-Ion Magnets with mer-Directing Ligands but Ambiguous Coordination Geometry.

Yan Peng1,2, Valeriu Mereacre1, Christopher E Anson1

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Inorganic Chemistry
|May 10, 2017
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Summary

Three new cobalt(II) complexes exhibit slow magnetic relaxation, a rare property for octahedral cobalt(II) single-ion magnets. Their unique coordination geometry challenges typical descriptions, showing characteristics of both octahedral and trigonal prismatic structures.

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Area of Science:

  • Inorganic Chemistry
  • Materials Science
  • Magnetochemistry

Background:

  • Cobalt(II) mononuclear complexes are investigated for single-ion magnet (SIM) properties.
  • Octahedral coordination geometry in Co(II) SIMs often correlates with positive zero-field splitting (ZFS) values.
  • Trigonal prismatic coordination geometry in Co(II) SIMs typically shows negative D ZFS values.

Purpose of the Study:

  • To synthesize and characterize novel air-stable cobalt(II) mononuclear complexes.
  • To investigate the magnetic properties, specifically slow magnetic relaxation, of these complexes.
  • To correlate coordination geometry with magnetic behavior and ZFS parameters.

Main Methods:

  • Single-crystal X-ray diffraction for structural characterization.
  • Direct and alternating current magnetic susceptibility measurements.
  • High-level electronic structure calculations and SHAPE program analysis for coordination geometry.

Main Results:

  • Three air-stable Co(II) complexes, [Co(H2L1)2]·2THF (1), [Co(HL2)2] (2), and [Co(H2L3)2]·CH2Cl2 (3), were synthesized.
  • All complexes exhibited field-induced slow magnetic relaxation.
  • Experimental and computational data indicated negative D ZFS values, suggesting trigonal prismatic geometry, despite a distorted octahedral mer coordination.

Conclusions:

  • The synthesized Co(II) complexes display slow magnetic relaxation, expanding the known examples for octahedral Co(II) SIMs.
  • The coordination geometry is ambiguous, exhibiting characteristics between octahedral and trigonal prismatic.
  • Negative D values align with trigonal prismatic geometry, but rhombicity complicates definitive assignment.