Dempsey, Scotty Lee (2014-05). Synthesis, Structure and Characterization Of Polynuclear Rare Earth Alkoxide Clusters. Doctoral Dissertation. Thesis uri icon

abstract

  • 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 Ln?(H-?TDCI)?(L) (Ln = Y, Eu, Gd, Tb, Dy, Ho, Er; L =MeOH, H?O, 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 (C?O?)?- and benzenedicarboxylate. The dysprosium clusters Dy?(H-?TDCI)?(MeOH)? and Dy?(H-?TDCI)?(dpm)? (dpm = dipivaloylmethanide) as well as the coordation polymer Dy?(H-?TDCI)?(C?O?)?/? 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 Gd?(??-O)(??-OH)?(??-O)?(PhB(OEt)?)?(dpm)?(HOEt)? and Gd?(??-O)(??-OH)?(dpm)? as well as the edg-bridged [Dy?(??-O)(??-OCH?CF?)??(OCH?CF?)?][Na(thf)?]?. All compounds were characterized by single-crystal X-Ray diffraction.
  • 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 Ln?(H-?TDCI)?(L) (Ln
    = Y, Eu, Gd, Tb, Dy, Ho, Er; L =MeOH, H?O, 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 (C?O?)?- and benzenedicarboxylate.

    The dysprosium clusters Dy?(H-?TDCI)?(MeOH)? and Dy?(H-?TDCI)?(dpm)? (dpm
    = dipivaloylmethanide) as well as the coordation polymer Dy?(H-?TDCI)?(C?O?)?/? 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
    Gd?(??-O)(??-OH)?(??-O)?(PhB(OEt)?)?(dpm)?(HOEt)? and Gd?(??-O)(??-OH)?(dpm)? as well as the edg-bridged [Dy?(??-O)(??-OCH?CF?)??(OCH?CF?)?][Na(thf)?]?. All compounds were characterized by single-crystal X-Ray diffraction.

publication date

  • May 2014