DESIGN AND SYNTHESIS OF SELF-ASSEMBLING SUPRAMOLECULAR CAGES BASED ON TPMA LIGANDS

This thesis presents the synthesis and characterization of novel TPMA-based supramolecular amine cages, derived from the reduction of their imine counterparts. The work focuses on four new structures with varying diamine linkers, optimizing the synthetic procedure and work-up methods. The amine cages were successfully complexed with Zinc(II) and Cobalt(II), and the resulting complexes were thoroughly characterized using various spectroscopic techniques. The molecular recognition properties of the zinc complexes were investigated through ESI-MS competition experiments, revealing their ability to encapsulate a range of dicarboxylic acids. Compared to their imine analogues, the amine cages demonstrated reduced selectivity in guest binding, attributed to their increased conformational flexibility. The cobalt complexes were evaluated as catalysts for the Hydrogen Evolution Reaction (HER). These systems proved capable of generating hydrogen in quantitative amounts, with catalytic activity enhanced by elongation of the diamine linker. The performance of these novel catalysts was compared to the previously studied Diaza-cope rearranged cage 10, showing comparable robustness but significantly increased quantum yield. This work demonstrates the potential of these new amine-based supramolecular structures in molecular recognition and catalysis, opening avenues for further research in these fields. The study highlights the impact of structural modifications on both host-guest interactions and catalytic efficiency, providing valuable insights for the design of future supramolecular catalysts.