Emulating natural photosynthesis Self-assembled cage scaffolds to control molecular aggregation states

Artificial photosynthesis is a global scientific endeavour that attempts to develop solar-to-fuel devices as a viable approach to sustainable energy production and storage. Inspired by Nature’s strategies, a case is made for organization of molecules on a self-assembled scaffold. At the same time, porphyrins are recognized for their potential in supramolecular chemistry and artificial photosynthesis because of their excellent light-harvesting and catalytic properties. A metal-mediated self-assembly strategy forms porphyrin-equipped M_nL_2n coordination cages. This thesis investigates what properties of natural photosynthesis can be emulated by application of M_nL_2n supramolecular cages equipped with porphyrins. Thus, two hallmark objects of supramolecular chemistry — porphyrins and supramolecular coordination cages — have been combined to obtain self-assembled systems with potential application in controlled energy transduction and catalysis. By focussing on light-harvesting and on the organization of chromophores, these porphyrin-equipped cages are introduced as a new, powerful tool in the box of supramolecular chemistry.