A Reversibly Porous Supramolecular Peptide Framework

The ability to use bio‐inspired building blocks in the assembly of novel supramolecular frameworks is at the forefront of an exciting research field. Herein, we present the first polyproline helix to self‐assemble into a reversibly porous, crystalline, supramolecular peptide framework (SPF). This framework is assembled from a short oligoproline, adopting the polyproline II conformation, driven by hydrogen‐bonding and dispersion interactions. Thermal activation, guest‐induced dynamic porosity and enantioselective guest inclusion have been demonstrated for this novel system. The principles of the self‐assembly associated with this SPF will be used as a blueprint allowing for the further development of helical peptide linkers in the rational design of SPFs and metal‐peptide frameworks.