Dempsey, Scotty Lee (2014-04). 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 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(u6-O)(u3-OH)6(u3-O)2(PhB(OEt)2)2(dpm)6(HOEt)2 and Gd6(u6-O)(u3-OH)8(dpm)8 as well as the edg-bridged [Dy6(u6-O)(u2-OCH2CF3)12(OCH2CF3)6][Na(thf)6]2. All compounds were characterized by single-crystal X-Ray diffraction.

publication date

  • May 2014