The photoisomerization properties of single azobenzene subunits with imine moieties, A1 and A2 (Fig. ), were also characterized to determine the influence of cage formation on both the PSS and thermal half-life in dry DCE (ca. 30 μM) (Fig. ). Interestingly, the single azobenzene unit A1 showed lower conversion for both E→Z (65% vs 77%) and Z→E (87% vs 94%) photoswitching over ACC-1, whilst A2 displayed a higher conversion for E→Z (80% vs 54%) and Z→E (94% vs 97%) than ACC-2. This suggests that there is a structural effect in the cage which influences the switching. The impact of cage formation on the thermal half-life did not affect the photoswitches similarly. At 25 °C, A1 displayed a half-life of 220 ± 70 hours-approximately double that of ACC-1 (i.e., cage formation resulted in a less stable Z-isomer), while A2 had a half-life of 4.78 ± 0.01 hours, meaning that cage formation improved the overall Z-isomer stability. A summary of the photoswitching properties is provided in Table , alongside their overall enthalpy (∆H ‡ ) and entropy (∆S ‡ ) of activation obtained via Eyring plots at elevated temperatures, though caution should be applied in the physical interpretation of the transition state parameters as the ZZZ→EEE conversion is a result of multiple sequential isomerization processes. The thermally induced isomerization of EZZ to EEZ has the longest half-life, which correlates with the comparatively smaller difference in relative energy of the photoisomers (Fig. ).