Cagelike Octacopper Methylsilsesquioxanes: Self-Assembly in the Focus of Alkaline Metal Ion Influence-Synthesis, Structure, and Catalytic Activity.

A family of unusual octacopper cage methylsilsesquioxanes - were prepared and characterized. Features of their cagelike (prismatic) structure were established using X-ray diffraction studies. Effects of distortion of prismatic cages - due to variation of (i) additional alkaline metal ions (K, Rb, or Cs), (ii) combination of solvating ligands, and (iii) nature of encapsulating species were found. Opportunities for the design of supramolecular 1D extended structures were found. These opportunities are based on (i) formate linkers between copper centers (in the case of CuK-based compound ) or (ii) crown ether-like contacts between cesium ions and siloxane cycles (in the case of CuCs-based compound ). CuCs-complex was evaluated in the catalysis of alkanes and alcohols. Complex exhibits high catalytic activity. The yield of cyclohexane oxidation products is 35%. The presence of nitric acid is necessary as a co-catalyst. The oxidation of alcohols with the participation of complex as a catalyst and tert-butyl hydroperoxide as an oxidizer also proceeds in high yields of up to 98%.