Construction of a π-stacked supramolecular framework using a triphenylene-cored metallo-organic cage

Abstract

Supramolecular nanocages with inner cavities have attracted increasing attention due to their fascinating molecular aesthetics and vast number of potential applications. Even though a wide array of discrete supramolecular cages with precisely designed sizes and shapes have been established, the controlled assembly of higher-order supramolecular frameworks from discrete molecular entities still represents a formidable challenge. In this work, a novel metallo-organic cage [Zn₁₂L₄] was assembled based on a triphenylene-cored hexapod terpyridine ligand. Synchotron X-ray analysis revealed a pair of enantiomeric cages in the crystal with flexible ligands twisted clockwise or anticlockwise due to steric hindrance in the structure. Interestingly, due to the strong π–π intermolecular interaction between triphenylene units, a controlled hierarchical packing of sphere-like cages in the crystal was established having a sparse packing mode with huge channels of around 3.6 nm diameter. This research sheds light on the design of strong π–π interactions in supramolecular hierarchical packing and materials science.