Polymorphism and flexibility of six-porphyrin nanorings in the solid state

Butadiyne-linked porphyrin nanorings are fascinating nanometer-sized platforms for exploring electronic delocalization and aromaticity, and they mimic ultra-fast photosynthetic energy-transfer phenomena in plants and purple bacteria. However, little is known about how they interact in the solid state. Here, we compare the crystal structures of several pseudopolymorphs of a six-porphyrin nanoring template complex, and report the structure of the free-base nanoring co-crystallized with C₆₀. The structures differ not only in the molecular packing; they also feature different molecular conformations. The template is slightly too small for the cavity of the nanoring, and this size mismatch can be accommodated by two types of distortion: either the zinc atoms are pulled away from the planes of the porphyrins, or the nanorings contract by adopting a ruffled conformation, with butadiyne links alternatingly above and below the plane of the six zinc centers. The template-bound ring forms sheets and tubular stacks with interdigitated aryl groups. Upon demetallation, the nanoring becomes more flexible, adopting a highly elliptical conformation on co-crystallization with C₆₀. The structure of this free-base nanoring features infinite solvent filled channels with a channel diameter of 13.5 Å. The high porosity of these materials points towards possible applications as porous light-harvesting frameworks.