Analysis of rotaxanes 10 and 11. Rotaxanes (Em,Sco-c)-10 and (Zm,Sco-c)-10 have distinct 1 H NMR spectra (Figures and respectively) that each correspond to one of the inseparable isomers obtained using a direct AT-CuAAC approach to the same molecules (c.f., 4, see ESI section 4) (Fig- ). Rotaxanes 11 present much higher symmetry 1 H NMR spectra than those of rotaxanes 10 but not because the macrocycle preferentially encircles the amine unit; the high chemical shift of triazole protons Hh is consistent with the macrocycle exchanging between the two triazole containing compartments where it engages in a C-H•••N H-bond. Instead, and in contrast with MAC rotaxanes, 5 based on a similar prochiral axle, the two co-conformers of rotaxanes 11 are enantiomeric and so the Hh pair are enantiotopic. Interestingly, the absolute stereochemistry of the co-conformations of rotaxane 11 (Scheme 3), and that of static diastereomers 4 and 10, can be fully described using two of three possible stereolabels, of which we strongly prefer the co-conformational covalent and MGI-2 description as this captures the desymmetrization of the axle component upon shuttling and the fixed stereogenic unit of the molecule. The co-conformational MPC/MGI-2 description fails to capture the former and the co-conformational covalent/co-conformational MPC description obscures the fixed MGI-2 unit, with both stereolabels inverting under co-conformational exchange (see ESI section 5 for an extended discussion). Scheme 3. Co-conformational isomerism in rotaxane (Zm)-11 highlighting the different stereochemical labels that can be applied to fully assign their absolute configuration.