Initially a computational screen was carried out with the aim of predicting a priori viable POCs that incorporate an azobenzene switch. Two azobenzene precursors were identified from the screen based on existing precursor scaffolds previously used in POC syntheses, and their synthetic viability assessed based on known routes to azobenzenes, where the azobenzene was incorporated into the scaffold rather than as a pendant group. This resulted in ditopic and tetratopic aldehydes that were assembled computationally in both their E-and Z-conformations with seven ditopic and three tritopic amines into a range of candidate organic cages. This included three cages in each of the Tri 2 Di 3 and Tri 4 Di 6 topologies for the ditopic aldehydes with tritopic amines, and seven cages in each of the Tet 2 Di 4 and Tet 3 Di 6 topologies for the tetratopic aldehydes with ditopic amines, where the superscripts signify the number of each of the precursors incorporated into the cage (Fig. ). For the tetratopic aldehyde systems, there are multiple connection possibilities, depending upon the relative arrangement of the tetratopic aldehyde. This means there are 2 positional isomers to consider for each Tet 2 Di 4 topology and 4 for each Tet 3 Di 6 topology. Thus, a total of 48 possible cages were modelled. After structural model assembly using our supramolecular toolkit (stk) software package, the OPLS3e forcefield was used to geometry optimise each cage, and a basic conformer search was carried out using gas-phase molecular dynamics (MD) simulations where 50 conformations were sampled over 200 ps. During this process, the torsion angles across the diazene moiety were constrained to prevent conversion between the E-and Z-isomers. The lowest-energy candidate cages were screened for shape-persistence and symmetry using pyWindow, open-source code for the determination of cavity size, the number of windows and diameter of windows for porous molecules. The resulting cages were then inspected to identify promising candidates on the basis of being shape-persistent (having an internal cavity that can fit a sphere of diameter greater than 1 Å) and being largely symmetric (i.e., all window diameters within 10% of each other). As a further filter, we visually inspected the structures to prioritize candidate molecules that were not overly strained; for example, by containing out-ofplane imine bonds. Cages where both the fully trans (EEE) and fully cis (ZZZ) forms satisfied the above criteria were hypothesised to be potentially photoisomerizable, not considering at this point energy barriers to interconversion. In general, the tetratopic diazene aldehyde was found to be more likely to form a photoisomerizable cage than the ditopic diazene aldehyde. This was also promising because it suggested the potential for a larger structural photoresponse, since the Tet 3 Di 6 topology results in larger molecular cages with more photoisomerizable linkers. Based on this computational screening, both the ditopic and tetratopic aldehyde were investigated experimentally.