The rise of molecular engineering in recent years has been well documented in the form of fabrication of sophisticated molecular motifs and nanostructured architectures. These have found a multitude of applications throughout the scientific disciplines and examples include: tailored macrocycles and supramolecules, molecular machines, nanomaterials, designer proteins, etc. In many cases, joint effort projects were started at the intersection of engineering, medicine, biology, physics and chemistry. Consequently, multiple fields were advanced simultaneously, which accounted for the propagation of molecular engineering and for the dissolution of borders throughout the scientific community.<br/>Combining classic synthetic organic chemistry with concepts found in engineering and architecture, previously unknown organocatalysts have been designed based on distorted porphyrins. In this project, the opportunities provided by molecular engineering were exploited and merged with an 'architect's approach' where spatial requirements and the 3D physical structure of the macrocycles were taken into consideration. Typically, the inner core system of porphyrins is not involved in intermolecular interactions as it is 'buried' within the surrounding macrocycle. However, possibilities exist to utilize the bifunctional core and to allow for the activation of small molecules. By reshaping the vector of the central N/N–H groups outwards, the imine moieties became increasingly basic while the amine groups started to engage in hydrogen bonding. This resembled a molecular redesigning process that introduced nonplanarity into the porphyrin architecture and rendered them catalytically active. Altogether, the interplay of an organic chemical skill set and approaches found in engineering and architecture created a synergistic effect that allowed us to open a new avenue in organocatalysis and new functional roles for tailor-made porphyrins alike.

Am I a chemist, an engineer, or an architect? How to redesign natural porphyrins as organocatalysts

2019 Spring National Meeting

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