Porous materials have applications in processes such as petrochemical refining and the separation of gases and solvents. In recent years, multicomponent self-assembled materials have emerged as an important class of porous materials. This includes porous coordination polymers and metal-organic frameworks (MOFs) formed through coordination chemistry, and covalent-organic frameworks (COFs) and porous organic cages (POCs) typically formed using dynamic covalent chemistries, such as imine condensations. POCs are 3-dimensional discrete organic molecules that contain a permanent internal cavity that is accessible through multiple windows. POCs can be formed into molecular solids, but lack the extended coordination or covalent bonding networks found in MOFs and COFs. However, POCs can pack together in the solid-state to form interconnected pore networks, and they have shown potential in the molecular separation of gases, hydrogen isotopes, and organic compounds. 9 Additionally, POCs have been used as molecular sensors, and due to their discrete nature and solution processability, they have been incorporated into a new generation of porous materials known as porous liquids; that is, liquids that contain permanent intrinsic porosity. The integration of stimuli-responsive moieties into porous materials such as MOFs and COFs can result in materials that are capable of a structural switch between two or more isomeric states. To induce a response, the energy input can be by photochemical irradiation, 13 mechanical stress, or electrostatic stimulation. There are several benefits to incorporating stimuli-responsive functional groups in a porous material, including the ability to change the internal pore size allowing for on/off selectivity of gases, or to spontaneously release gas from within the porous material, or to block the pore windows enabling gas storage through a trapping technique. 17 Several compounds undergo isomerization upon irradiation with UV-visible light (photoisomerization), including stilbenes, azobenzenes, 19 diarylethenes, spiropyrans, and imines. Here, azobenzenes were selected for their reversible E-Z isomerization (Fig. ) which can have a dramatic effect on the molecular geometry of the species they are incorporated into, compared to the more subtle bond rearrangements found in diarylethenes. 13b Azobenzenes' resistance to photodegradation makes them suitable for multiple uptake/release photoswitching cycles in porous materials compared to stilbenes and spiropyrans. There are several methods by which these photoresponsive moieties can be integrated into a porous material (Fig. ). The first method includes addition of a photoresponsive guest -that is, a porous material is loaded with a photoactive guest (Fig. (i)) and upon irradiation, a change is imposed on the host material. Another method is the incorporation of photoresponsive auxiliaries (Fig. (ii)). This second method typically has minimal effect in relation to a structural change, but rather, the pore can be filled, or the windows can be blocked or opened, through an E-Z isomerization. A third method of integrating a photoresponsive group is to incorporate it directly into the molecular structure itself (Fig. (iii)); for example, by the addition of photoresponsive linkers into a MOF. While the incorporation of photoswitchable moieties into coordination cages and macrocycles has been reported, the formation of stimuli-responsive POCs remains underexplored. Previous literature has focused on POCs formed exclusively from ditopic azobenzene precursors, linked either via imine or amine functionalities with examples demonstrating improved photostationary states upon POC formation, 31 differential reactivity towards imine exchange reactions upon switching, and p-xylene separation through a crystal-to-crystal phase transition. Oshchepkov et al. studied the ability of the same amine-linked cage for anion coordination and recognition by a larger cucurbit [8]uril host. It can be envisaged that the introduction of a photoresponsive moiety into a POC could result in a dynamic reversible geometry change, leading to a controllable pore size and shape, which in turn might enable host-guest selectivity or the controlled uptake and release of different molecular guests in the cage.