A preliminary synthetic investigation was carried out into the cage formation between the tetratopic diazene aldehyde (for synthetic routes to precursors, see SI Section 2) in combination with (1R,2R)cyclohexyldiamine (CHDA), using conditions similar to those previously reported for analogous tubular covalent cages (TCC1-3). In this initial screen, both solvent and concentration were varied, using conditions previously reported in a high-throughput automated synthetic cage screen (Table ). 35b Reactions were conducted in deuterated solvents to allow direct analysis prior to isolation. Species remained in solution under all conditions investigated and 1 H NMR analysis confirmed that all reactions had gone to completion and formed a single molecular species. In each case, high-resolution mass spectrometry (HRMS) indicated clean formation of a Tet 3 Di 6 cage species. Following this successful cage formation, the remaining 6 ditopic amines from the computational modelling were screened (Table ), with the aim of incorporating a more flexible diamine into the cage structure, as it was thought that the highly pre-configured CHDA linker could potentially prevent the cage from having enough rotational freedom to photoisomerize. However, many of the ditopic amines screened resulted in precipitates forming over the course of the reaction, suggesting that insoluble polymer was formed -this disrupts the equilibrium of species in solution and reduces the amount of cage that can be formed in the reaction, if any cage was formed. In all of these cases, analysis by 1 H NMR spectroscopy indicated either the reaction had not gone to completion or no soluble molecular species were present. However, HRMS indicated trace formation of a further three Tet 3 Di 6 cages, alongside a Tet 2 Di 4 cage that formed with 1,3-diaminopropane (Table ).