Chalcogen-rich lanthanide clusters with fluorinated thiolate ligands

Area of Science:

• Organometallic Chemistry
• Lanthanide Chemistry
• Coordination Chemistry

Background:

• Lanthanide complexes with chalcogenide ligands are of interest for their unique electronic and structural properties.
• Fluorinated ancillary ligands can influence the stability and reactivity of metal clusters.
• Understanding the formation and structure of chalcogen-rich lanthanide clusters is crucial for developing new materials.

Purpose of the Study:

• To synthesize and characterize novel chalcogen-rich clusters incorporating fluorinated thiolate ligands.
• To elucidate the structural features of these clusters using X-ray diffraction.
• To explore the extension of this cluster chemistry to redox-inactive lanthanides.

Main Methods:

• Reaction of lanthanide precursors with elemental sulfur or selenium.
• Low-temperature single-crystal X-ray diffraction for structural determination.
• Synthesis and characterization of Ytterbium (Yb) and Thulium (Tm) complexes.

Main Results:

• Successful synthesis of chalcogen-rich clusters with the general formula Ln(SC(6)F(5))(3) and Ln(EPh)(3) (E = S, Se).
• Structural determination of (THF)(6)Yb(4)S(SS)(4)(SC(6)F(5))(2) and (THF)(6)Yb(4)Se(SeSe)(4)(SC(6)F(5))(2), revealing a square Yb(4) core.
• Preparation of the redox-inactive complex (THF)(6)Tm(4)Se(SeSe)(4)(SC(6)F(5))(2), demonstrating broader applicability.

Conclusions:

• The study presents a new class of chalcogen-rich lanthanide clusters with fluorinated thiolate ligands.
• The unique square Yb(4) array structure provides insights into lanthanide cluster formation.
• The demonstrated synthesis of both redox-active and redox-inactive lanthanide clusters expands the scope of this chemistry.