Synthese And Property Study Of Decatungstate Hybrid Material And Sulfonatocalix[4]arene Supramolecular Compounds

The aim of this thesis is the synthesis of new compounds on the basis of [W₁₀O₃₂]4- polyoxoanion clusters or p-sulfonatocalix[4]arene, which are bridged by various metals. The study on synthetic conditions and rules for these four new compounds are also carried out and the four compounds were structurally characterized by elemental analyses, IR, TG, CV and single crystal X-ray diffractions.1. The assembly of decatungstate isopolyanion [W₁₀O₃₂]4- and the [Ce(H₂O)(DMF)6]4+ complex fragments lead to the formation of new compound [Ce(H₂O)(DMF)6(W₁₀O₃₂)](DMF) (CH3CH₂OH) (1) that exhibits an unusual one-dimensional helical structure constructed by rare quadrivalent cerium-linking decatungstate building blocks.2. Two copper–organic framework supramolecular assemblies of p-sulfonatocalix[4]arene and 1,10-phenanthrolin Cu2[C₁₂H₈N₂][C₂₈H₂0S₄O₁₆][H₂O]23.5 (2) and Cu3[C₁₂H₈N₂]3[C₂₈H19S₄O₁₆]Cl[H₂O]17.6 (3) were obtained by pH-dependent synthesis at room temperature. Both structures show 1D water-filled channels (rectangular shape in 2 and triangular in 3) with the solvent-accessible volume occupying 30.8% (2) and 24.2% (3) of the unit-cell volume, respectively. The calixarene molecules in both structures assume analogous cone shapes of C2V symmetry instead of the conventional C4V symmetry. Their connecting to different amounts of copper/phenanthroline cations leads to the formation of different structures.3. A supramolecular complex Zn2[C₁₂H₈N₂]2[C₂₈H₂0S₄O₁₆][H₂O]17.7 (4), has been synthesized under hydrothermal conditions, and characterized by IR spectroscopy, TG and DTA analysis, and single crystal X-ray diffraction. Unprecedented (H₂O)10 water clusters consisting of cyclic pentamer (H₂O)5 and five dangling water molecules were observed in the lattice.