Catenanes consist of two or more entangled rings forming a mechanically interlocked chain, while rotaxanes and shuttles typically consist of one or more macrocyclic rings mechanically interlocked around a dumbbell-shaped molecule (the axle) with two bulky groups at both ends (stoppers). In rotaxanes, the macrocycles can move back and forth along the axle, and we take the liberty to describe this translational movement as "shuttling". The same type of linear movement occurs also in the so-called "molecular shuttles", while the fundamental difference of a shuttle (as opposed to a simple rotaxane) is that there are at least two distinct binding sites for the ring within the thread, such that there is not one single global thermodynamic minimum for the stochastic location of the ring (but at least two local minima). As a relevant example, Green et al. designed a monolayer of bistable molecular switches as a storage element, relating the relaxation kinetics with the memory retention time of the device. Significant breakthroughs were also achieved, for example, in catalysis, exploiting the threading of the macrocycle along the thread to expose/hide organocatalytic groups, or in drug delivery, where the controlled disassembly of a biocompatible [2]rotaxane was exploited to trigger the release of anticancer drugs. Designing MIMs with controllable dynamical properties could benefit from a deeper understanding of the factors controlling their structure and dynamics. In particular, reaching a molecular understanding of rotaxane dynamics in solution and unraveling the details of the mechanisms (thermodynamics and kinetics) underpinning their behavior is crucial for designing MIMs with desired properties. Experimental investigations based, for example, on nuclear magnetic resonance, coalescence methods, or cyclic voltammetry allowed for estimating the dynamics of rotaxanes and molecular shuttling. For example, the influence of the axle length, the conformational flexibility of spacers and of different environments on the shuttling rate constants were extensively investigated. However, the spatio-temporal resolution of such kinetic experiments is typically limited, which makes it difficult to obtain direct information on the molecular factors that control the dynamics of these systems. To this end, it would be necessary to study the dynamics of the MIMs at a sub-molecular resolution.