Design and synthesis of porphyrinic metal-organic frameworks

Metal-organic frameworks (MOFs), are a new class of crystalline materials consisting of organic linkers and inorganic connectors, and have gained considerable interest in recent years. This dissertation is focused on the rational design and synthesis of twelve novel MOFs using porphyrinic building blocks and paddlewheel metal clusters. The studies are based upon a synthetic strategy to achieve the materials through new porphyrinic linkers, combined with porphyrin paddlewheel frameworks (PPFs). The extension of pillar length affects differently depending on the incorporated porphyrin metal. Various topologies (bilayer, AA interpenetration, ABBA) were obtained with MOFs constructed from zinc-metallated porphyrins. However, if cobalt-metallated porphyrins were used, the stacking of the framework was fixed to AB pattern regardless of the pillar size. The modification of the porphyrin building blocks generates different type of frameworks. The linear ditopic porphyrin ligand with BPY pillar created a T-shaped linker, resulting in a rare anatase topology. The expansion of the porphyrin size produced 2D porphyrin sheets with intermolecular C-H/···π interactions between the layers. Substitution of the porphyrin with meta carboxyl groups resulted in a new type of non-pillared porphyrinic framework with polyhedral cages were formed