The thermal properties of the cage[n]rotaxanes (Table ) were studied using thermogravimetric analysis (TGA) and optical differential scanning calorimetry (DSC) after activating the samples to remove solvent. The decomposition temperatures (Td) for non-interlocked A1-A3 increased with the number of triazole units from 170 °C (A1) to 220 °C (A3). In comparison, the rotaxanes CR1-CR3 all showed lower Td values, with limited variation between the different systems (150-160 °C). In contrast to the non-interlocked axles, which all decomposed prior to melting (Fig. , S113 and S126), each of the rotaxanes was observed to partially melt (Fig. , S155 and S169), with this process occurring over a broad temperature range of 10-20 °C, a feature previously observed with other reduced organic cages. The apparent degree and onset of melting increased with the number of interlocked components, suggesting the incorporation of the macrocycle, which itself melts at ~100 °C with a sharp endotherm (Fig. ), is leading to this observed behaviour. We subsequently shifted our focus to carrying out gas sorption studies (Fig. ), comparing the alkynefunctionalised cages (C1-C3), non-interlocked axles (A1-A3), and rotaxanes (CR1-CR3). Due to the difficulties in purifying large quantities of the cage[n]rotaxanes, we performed these on the bulk amorphous samples which, after removing residual azide and macrocycle from the crude material, contained quantities of non-interlocked axle and/or partially rotaxanated products (14, 7 and 31 mol% for CR1, CR2, and CR3, respectively; see Fig. ). While the rotaxanes all exhibited no porosity to N2 (77 K, 1 bar) based on their Brunauer-Emmett-Teller (BET) surface areas (4.9, 12.8 and 1.7 m 2 /g for CR1, CR2, and CR3, respectively), due to the presence of the free amines in the cage structures, we turned our attention to CO2 uptake under standard conditions (298 K, 1 bar). Interestingly, C3 displayed much higher CO2 uptake (0.35 mmol g -1 ) compared to C1 and C2 (0.12 and 0.06 mmol/g, respectively). A1-A3 showed enhanced uptake over their respective alkyne precursors, and increased adsorption values with each additional triazole unit (0.42, 0.53 and 0.68 mmol g -1 for A1, A2 and A3, respectively). As C1-C3 and A1-A3 have chemically identical cavities, they would be expected to have the same intrinsic porosity. Therefore, the observed trends in CO2 uptake are likely to be due to increased extrinsic porosity resulting from poor packing efficiency of the bulky di-tert-butylphenyl stopper units. Finally, the rotaxanes CR1-CR3 also showed enhanced uptake with an increasing number of substituents (0.17, 0.19 and 0.26 mmol g -1 , respectively); however, these values were consistently lower than their non-interlocked counterparts. We surmise that this is likely a result of the macrocyclic components occupying the void spaces created by the bulky stopper units, reducing the available extrinsic porosity. In addition, the simulated structures indicate that the macrocyclic components could limit the free space surrounding the amine groups in the cage scaffold. This would additionally frustrate the coordination of CO2 molecules with the amine sites, reducing the CO2 sorption capacity of the materials containing more macrocyclic components. As has been previously demonstrated, inter-component interactions can result in MIMs possessing drastically different solubilities compared to their individual non-interlocked components. Consequently, we sought to investigate how the mechanically appended bipyridyl macrocycles affected the solubilities of the cages (Fig. ), as this is an important factor when processing these species into mixed-matrix membranes and porous liquids. The non-interlocked cage axles (A1-A3) all displayed similar solubilities (~0.08 M) in chloroform that were greater than their precursor alkyne cages (C1-C2). A further notable enhancement was observed for the rotaxane structures (CR1-CR3), with each displaying solubilities of ~0.13 M. Thus, the presence of M (itself displaying high solubility of 0.82±0.032 M) significantly enhanced the solubility of the rotaxanes compared to the non-interlocked cages.