Initially, we confirmed the viable reactivity of the alkyne units through reaction of C1-C3 with S under standard CuAAC conditions (CuSO4•5H2O, sodium ascorbate, DMF, RT). Pleasingly, each of the non-interlocked axle cages with 1-3 triazole units (A1-A3, respectively) was obtained in good isolated yield (38-64%). Subsequently, each of C1-C3 was submitted to CuAAC-AMT conditions which, following column chromatography, yielded the target [2]-, [3]-, and [4]rotaxane structures (CR1, CR2 and CR3, respectively) in quantities >100 mg. This bulk material was contaminated with small amounts of non-interlocked triazole components that could be quantified by 1 H NMR spectroscopy (Fig. ). Due to difficulties in separating the interlocked and non-interlocked components by standard chromatographic techniques, isolation of the pure rotaxanes CR1, CR2 and CR3 required reverse-phase preparative TLC, giving the interlocked structures in isolated yields of 10%, 13% and 28%, respectively. Such purification techniques, however, limited the amount of pure CR products that could be brought through (<30 mg). Successful rotaxane formation was confirmed by HR-ESI-MS and NMR spectroscopy (Fig. ). In particular, characteristic shifts in 1 H NMR spectral peaks compared to the non-interlocked axle (A1-A3) and macrocycle (M) components supported the formation of the target interlocked structures. For example, the downfield shift of the triazole resonance (He) in rotaxane CR1 compared to the non-interlocked axle A1 (Δδ = 2.31 ppm; Fig. and) was indicative of C-H•••N hydrogen bonding between the triazole and bipyridyl unit of the macrocycle, as previously observed in related systems. Cage[n]rotaxanes CR2 and CR3 (Fig. and, respectively) displayed similar resonance shifts compared to their non-interlocked components. Disappointingly, despite multiple attempts, we were not able to grow X-ray quality single crystals of any of the cages to confirm their structure in the solid-state. With the target cage[n]rotaxanes in hand, we looked to investigate how the properties of the interlocked structures differed from their non-interlocked counterparts. In this regard we investigated the thermal properties, CO2 uptake, and solubilities of the cages, axles and rotaxanes.