Photoresponsive Supramolecular Cages and Macrocycles

The utilisation of light to achieve precise manipulation and control over the structure and function of supramolecular assemblies has emerged as a highly promising approach in the development of complex, configurable, or multifunctional systems and nanoscopic machine-like entities. In this minireview, we highlight recent examples of self-assembled and covalently bound cages and macrocycles with a focus on the external and internal functionalisation of a structure with a photoswitchable unit or the embedment of a photoswitch into the framework of a structure. Functionalising the interior or exterior of a supramolecular cage or macrocycle with a photoresponsive group enables control over different properties, such as guest binding or assembly in the solid-state, while the overall shape of the assembly often undergoes no significant change. By directly integrating a photoswitchable unit into the framework of a supramolecular structure, the isomerisation can either induce a geometry change, the disassembly, or the disassembly and reassembly of the structure. Historical and recent examples covered in this review are based on azobenzene, diarylethene, stilbene photoswitches, or alkene motors that were incorporated into macrocycles and cages constructed by metal-organic, dynamic covalent, or covalent bonds.