Cage-controlled light-driven catalysis

Photocatalysis provides complementary reactivity to traditional synthetic methods, which can be used to make chemical synthesis more sustainable and efficient. As such, a surge of interest over the last two decades has resulted in new synthetic procedures that are useful for academia and industry. However, many of these methodologies still suffer from fundamental problems that limit their application such as photon-to-product efficiency, and a limited pool of photocatalysts with long excited state lifetimes. Nature shows that preorganization of quenching components is key to achieve photochemical reactivity faster than diffusion, allowing short-lived excited states while limiting recombination. Utilizing these principles potentially opens up opportunities in various areas of photocatalysis, such as photocatalyst design, improved photon-to-product efficiency, (enantio-)selective photocatalysis, and challenging redox reactions. The focus of this thesis is therefore the utilization of supramolecular coordination cages in photocatalysis inspired by natural principles applied to synthetic systems. We showed that using these strategies, the C–H arylation of pyrroles has improved chemoselectivity and decarboxylation reactions at benzylic positions can occur at low concentrations and with short excited state lifetimes. The excitation wavelength can be tuned by ligand design which allowed red light photocatalysis of sulfonylazides. Finally, by coupling the photochemical decarboxylation reaction to a fueled equilibrium, temporal dependence of inputs emerged, which is a property neurons also possess. Together this thesis provides platforms to develop photocatalysis with coordination cages and highlights the benefits and opportunities of combining supramolecular principles with photocatalysis.