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This study introduces novel rare earth multidecker sandwich complexes, including the first triple-decker compounds with a cycloheptatrienyl ring. These complexes exhibit unique magnetic properties and ligand arrangements.

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Area of Science:

  • Organometallic Chemistry
  • Rare Earth Chemistry
  • Coordination Chemistry

Background:

  • Multidecker sandwich complexes are of interest for their unique electronic and magnetic properties.
  • Rare earth elements offer diverse coordination possibilities due to their f-electrons.
  • Cycloheptatrienyl (Cht) and cyclooctatetraenyl (Cot) ligands are versatile in organometallic chemistry.

Purpose of the Study:

  • To synthesize and characterize novel organometallic multidecker sandwich complexes featuring rare earth elements.
  • To explore the coordination chemistry of cycloheptatrienyl (Cht) and substituted cyclooctatetraenyl (CotTIPS) ligands with YIII and ErIII.
  • To investigate the magnetic properties of the synthesized ErIII complexes.

Main Methods:

  • Synthesis of inverse sandwich complexes using rare earth halides, tetrahydrofuran (thf), and borohydride.
  • Introduction of the 1,4-bis(triisopropylsilyl)cyclooctatetraenyl (CotTIPS) ligand to form triple-decker complexes.
  • Structural characterization and magnetic susceptibility measurements.

Main Results:

  • First structurally characterized organometallic multidecker sandwich complexes with a cycloheptatrienyl (Cht) ligand.
  • Isolation of unprecedented rare earth triple-decker complexes with a Cht ligand as the central deck and CotTIPS ligands.
  • Observation of antiferromagnetic coupling in ErIII congeners with a blocking temperature of 13.5 K.
  • Selective formation of a triple-decker complex with two differently substituted Cot ligands through ligand rearrangement.

Conclusions:

  • Demonstrated the feasibility of constructing rare earth multidecker sandwich complexes with purely carbon-based ligands.
  • Highlighted the versatility of Cht and Cot ligands in forming complex multinuclear rare earth structures.
  • Provided insights into the magnetic behavior of rare earth triple-decker complexes.