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F. Hamaz:
"Mono and Binuclear Copper(II) Complexes as Building Blocks for the Synthesis of Inorganic-Organic Hybrid Materials";
Supervisor, Reviewer: G. Kickelbick, W. Linert; Institut für Materialchemie, 2011; oral examination: 2011-04-05.

The combination of metal complexes with polymers can lead to novel hybrid materials which show structures that are determined by the polymeric backbone, the type of metal complexes, and their organization within the polymer matrix. Such polymers can be prepared either using metal complexes with polymerizable groups that are (co)polymerized with other monomers or by polymers that include functional groups attached to their chain which allow reactions with metal complexes.
In the first part of this work mononuclear, binuclear and polymeric copper(II) carboxylates were synthesized as building blocks for preparation of novel metal complex containing polymers. Binuclear copper(II) carboxylates were prepared either through the reaction of the corresponding carboxylic acid with basic copper carbonate or applying ligand substitution reactions to the available copper(II) carboxylates. The binuclear complexes contain polymerizable groups and coordinating sites which were occupied by apical ligands. In presence of an excess of strong donor ligands such as pyridine in the solution the binuclear structures of copper(II) carboxylates converted into mononuclear compounds. This route was used for preparation of mononuclear copper(II) carboxylates. Polymeric copper(II) carboxylates were prepared as 1-D polymeric chains using pyrazine or phenazine as linker between binuclear carboxylate units.
Polymers containing copper(II) carboxylates were synthesized through radical copolymerization of copper(II) carboxylates bearing polymerizable groups with methyl methacrylate using either azobisisobutyronitrile or benzoyl peroxide as initiator. The behaviour during copolymerization was investigated and a possible reaction mechanism was proposed.
In the second part of this work core-shell nanoparticles and structured hybrid materials were prepared, from organically modified silicon alkoxides, tetraetoxysiloxane and copper(II) carboxylates. Copper(II) methacrylate were self-assembled by the surface-functionalized with 4-pyridineethanamine, N-[2-(4-pyridinyl)ethyl]-N-[3-(triethoxysilyl)propyl] silica nanoparticles through Cu-N coordination interactions. Mixing copper laurate with the "4-Pyridineethanamine, N-[3-(triethoxysilyl)propyl] and tetraetoxysiloxane produced well-ordered mesostructured materials which were characterized by ordered pore structures and unique large surface area. These features make them very attractive as catalytic supports, adsorbents, hosts for nanomanufacturing