Dissertation: "Synthesis, Characterization and Reactivity of novel Bismuth-Corrole Derivatives"

In summary, synthesis and characterisation of differently substituted Bi-corrole complexes is described in this thesis. Starting with first metallation experiments under classical conditions, a novel metallation method for meso substituted corroles with Bi-trimethylsilyamide is introduced and the first crystal structure of a bismuth corrole is presented, which in many respects displays unique structural features. Further on, optimization of protocols for Suzuki cross coupling and Pd-catalyzed C-N coupling for corrole chemistry are described, so that the reactions work in regard of both, a broad substrate spectrum and gentle reaction conditions. This is followed by a general demetallation method, so that in total 18 new stable Bi-corroles and 16 of their demetallated counterparts were isolated. Photophysical, photochemical and photo-catalytic properties of selected derivatives are examined, but first and foremost electrochemical characterisation is presented and conclusions in regard to the underlying redox mechanisms are drawn.