Transition metal rimmed calixarenes and their supramolecular chemistry.

摘要

This thesis describes the design and the synthesis of novel anion and cation receptors in which sets of transition metal atoms are introduced on the rims of calixarene bowls.;A bowl-shaped calixresorcinarene 1 has been derivatized to incorporate either four phosphonite units to give a phosphonito-cavitand 2 or eight phosphinite units to give a phosphinito-calixresorcinarene 3. These derivatives have been used as multidentate ligands to incorporate transition metals on the upper-rim of the calixresorcinarene bowl. The chlorogold(I) complex of 4, 2(AuCl);The tetradentate phosphonito-cavitand, 2 has also been used in the synthesis of several tetracopper(I) and tetrasilver(I) complexes. The tetracopper(I) complex 5 and tetrasilver(I) complex, 6 have been shown to act as size-selective hosts for halide inclusion. Iodide is preferred over chloride as guest since it is large enough to coordinate to all four copper atoms in a unique ;Both the copper and silver complexes, 5 and 6 proved to be powerful and versatile metal cation receptors. The cation inclusions of 5 and 6 are driven by chelating effects of four chloride donors and enhanced by the occluded anion. X-ray analysis on 5;Tetra-O-alkyl-calix (4) arenes are shown to act as hosts for the