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Structural rearrangement through lanthanide contraction in dinuclear complexes.

Amy-Jayne Hutchings1, Fatemah Habib, Rebecca J Holmberg

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Summary
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New lanthanide complexes were synthesized, showing distinct structural types and magnetic properties. Complex 8, a dinuclear ytterbium (Yb) complex, demonstrates unique single-molecule magnet behavior with multiple relaxation processes.

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Area of Science:

  • Coordination Chemistry
  • Materials Science
  • Magnetism

Background:

  • Lanthanide ions offer unique magnetic properties suitable for advanced materials.
  • Schiff-base ligands provide versatile coordination environments for metal ions.
  • Understanding structure-property relationships in lanthanide complexes is key for developing new magnetic materials.

Purpose of the Study:

  • Synthesize and characterize a new series of lanthanide complexes.
  • Investigate the structural diversity and magnetic behavior of these complexes.
  • Explore potential single-molecule magnet properties.

Main Methods:

  • Schiff-base synthesis of the N'-(2-hydroxy-3-methoxybenzylidene)benzhydrazide (H2hmb) ligand.
  • Lanthanide complex synthesis and crystallization.
  • Single-crystal X-ray diffraction for structural determination.
  • Direct current (dc) and alternating current (ac) magnetic measurements.

Main Results:

  • Two distinct structural types of lanthanide complexes were obtained: Type I ([M(III)2(Hhmb)3(NCS)3]·2MeOH·py) and Type II ([M(III)2(Hhmb)2(NCS)4(MeOH)2]).
  • Type I complexes exhibit monocapped distorted square antiprismatic geometries, while Type II complexes show distorted dodecahedron geometries.
  • Complexes 5 (Dy), 7 (Er), and 8 (Yb) displayed slow relaxation of magnetization, indicating magnetic hysteresis.
  • Complex 8 is identified as the first dinuclear Yb-based single-molecule magnet with field-dependent multiple relaxation processes.

Conclusions:

  • The synthesized lanthanide complexes exhibit diverse structures and magnetic characteristics.
  • The study highlights the potential of lanthanide complexes as single-molecule magnets.
  • Complex 8 represents a significant advancement in the field of Yb-based single-molecule magnets.