Abstract

Metal-organic cages (MOCs) are functional host architectures of intense interest for applications in catalysis, sensing and stabilisation of reactive species, amongst others. The vast majority of MOCs reported employ symmetrical ligands to facilitate the self-assembly process, as lower symmetry ligands have the potential to form mixtures of isomeric products. Control of this self-assembly process, however, would allow access to more structurally sophisticated architectures, with implications for advanced functionality and guest-binding selectivity.

We have been interested in developing design strategies to bias the formation of particular MOC isomers from unsymmetrical ligand scaffolds. Towards this, we have successfully used covalent tethering as well as geometric and coordination-sphere design parameters to induce diastereoselective assembly of palladium(II)-based MOCs from ligands lacking bilateral symmetry. We have also begun to develop high-throughput computational methodologies to aid in the design of such systems, reducing costly trial-and-error synthetic discovery. Ongoing work is focused on extending our toolbox of design principles for accessing structurally complex, low-symmetry MOCs, and exploiting the observed correlation between experimental and computational results to allow in silico analysis for effective computational forecasting to aid in the design of future systems.