Synthesis, Structure and Characterization Of Polynuclear Rare Earth Alkoxide Clusters
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The versatile polyol/polyamine supporting ligand TDCI (1,3,5-tris(dimethylamino)- 1,3,5-trideoxy-cis-inositol was synthesized, and several lanthanide complex clusters of this ligand were produced.The coordination chemistry and characterization of these triangular lanthanide alkoxide clusters was explored. Molecular products include Ln₃(H−₃TDCI)₂(L) (Ln = Y, Eu, Gd, Tb, Dy, Ho, Er; L =MeOH, H₂O, dipivaloylmethanide, acetylacetonate, dibenzoylmethanide, tetraacetylethane, hexafluoroacetylacetonate).The dysprosium and gadolinium analogues of these clusters were used as secondary building units and were incorporated as preformed entities into coordination polymers linked by squarate (C₄O₄)²− and benzenedicarboxylate. The dysprosium clusters Dy₃(H−₃TDCI)₂(MeOH)₆ and Dy₃(H−₃TDCI)₂(dpm)₆ (dpm = dipivaloylmethanide) as well as the coordation polymer Dy₃(H−₃TDCI)₂(C₄O₄)₃/₂ were shown to exhibit slow relaxation of magnetization characteristic of single-molecule magnet behavior. The europium and terbium analogues were characterized by spectrofluorimetry. Hexanuclear oxo-centered Dy and Gd clusters were synthesized: the OH-face capped Gd₆(μ₆-O)(μ₃-OH)₆(μ₃-O)₂(PhB(OEt)₂)₂(dpm)₆(HOEt)₂ and Gd₆(μ₆-O)(μ₃-OH)₈(dpm)₈ as well as the edg-bridged [Dy₆(μ₆-O)(μ₂-OCH₂CF₃)₁₂(OCH₂CF₃)₆][Na(thf)₆]₂. All compounds were characterized by single-crystal X-Ray diffraction.
Dempsey, Scotty Lee (2014). Synthesis, Structure and Characterization Of Polynuclear Rare Earth Alkoxide Clusters. Doctoral dissertation, Texas A & M University. Available electronically from