De macrociclos a dendrimeros. Sintesis y aplicaciones

Resumen

In the first part of this research a new route to obtain macrocycle 4jjj and its optimization to make the synthesis on a multigram scale has been described. Starting from 4jjj, we have substituted the three fluorine atoms with -NR2 and -SR groups and we have formed the corresponding Pd(0) complexes in order to obtain catalysts soluble in ionic liquids and molecular materials useful as liquid crystals. The products obtained were not totally pure or they result inactive in the field of liquid crystals. In the second part of this research, three new families of phosphorus dendrimers have been synthesized. These dendrimers contain macrocycles on the surface, in the core or in both positions. As a result of the ability of the macrocycles to coordinate palladium(0) or platinum(0) atoms, dendrimers containing 3, 6, 12 and 96 macrocycles on the surface allow the preparation of the corresponding metal complexes, as well as several new nanoparticulated materials. The materials containing Pd(0) have been used as easily recoverable homogeneous and heterogeneous catalysts in Mizoroki-Heck reactions. Nanoparticles stabilized by a dendrimer that does not contain macrocycles on the surface have also been functionalized with iminophosphine groups coordinating palladium (II) atoms on the surface. When attempting to coordinate palladium and platinum(0) to the core of these dendrimers, we obtain nanoparticles and not the desired complexes. The last family of dendrimers obtained contains a macrocycle as core and 6 or 12 macrocycles on the surface. No metallic derivatives were prepared starting from these compounds. In order to obtain dendrimers with two different transition metals in their structures, we tried to build them using macrocycles already coordinating Pt(0). We tested the conditions starting from a dendrimer of zero generation. G0, but the resulting platinium(0) complexes were not stable during the condensation/reduction reactions used to synthetize these kind of compounds. Finally we analyzed some model structures in order to identify the parts of our dendrimers responsible for the formation of nanoparticles. No direct relation between the groups present in the structure of dendrimers and nanoparticles formation were observed.