Design, Self-assembly And Catalytic Property Of Triple-stranded Helicates

Helicates are of particular interest because they hold great potential in the construction of smart materials, devices and machines with programmed properties and functions. All these possible applications could undergo remarkable development if metal clusters exhibiting important physical, chemical and biological properties were incorporated into helicates. This thesis contains:1,A C2-symmetric hexadentate Schiff-base ligand of biphenyl was synthesized and successfully used to construct two heptanuclear cluster helicates [M7(OH)2L3] of zinc and copper;2,The helicates are stable in both solution and solid state and have been fully characterized by a variety techniques, including IR, UV-Vis, PL, NMR, ESI-MS, cyclic voltammetry and single-crystal X-ray diffraction;3,Both Zn and Cu compounds adopt triple-stranded cluster helicate structures and can be viewed as a linear hexanuclear triple-stranded helicate enclosing one metal ion in the cavity. The seven metal ions are engaged in two M7O4 distorted cubanes by sharing one metal ion, with a pair of terminal metal ions settle in two hydrophobic pockets that are generated by tert-butyl groups of the ligands.4,The Cu helicate could selectively catalyze the oxidation of C-H bonds of alkanes, which proceeds via a radical type mechanism. The selectivity may originate from the copper cluster featuring a helicate structure and a metal-centered hydrophobic pocket.