Having identified Z-azobenzenes as guests shifting the equilibrium towards C, we focused on encapsulating diazocine 5: an azobenzene, in which an ethylene bridge renders the Z isomer thermally stable. Figure shows Next, we hypothesized that rigidifying the guest might increase its affinity to C, thus further shifting the equilibrium towards the otherwise unstable isomer C. To this end, we switched to dibenzo[a,e]cyclooctene (DBCOT) 6, where 5's C-C single bond and the azo bond are replaced with C=C double bonds. Indeed, incubating the cage with solid 6 further increased the fraction of C to 72 mol%. Interestingly, the remaining 28 mol% of T showed no apparent affinity to 6 (which was used in excess), in contrast to Z-5 (Figure ). This observation suggests that the T→C transformation must not necessarily be preceded by the encapsulation of a guest by T (i.e., T + G → GÌT ⥂ GÌC; where G = guest); instead, the guest can template the formation of C from partially disassembled T. However, we cannot exclude an alternative scenario whereby the T→C reaction occurs via a hypothetical inclusion complex 6ÌT that forms with low yield (below the NMR detection limit).