Stepwise Dissipative Control of Multimodal Motion in a Silver(I) Catenate

Stepwise dissipative control of two distinct motions, i.e., shuttling and sliding, is demonstrated in a single multicomponent device. When [2]rotaxane 1, which acts as a biped, and deck 2 were treated with AgBF4/PhCH2Br+NEt3 as chemical fuel, the transient catenate [Ag(1)]+ ⋅ [Ag3(2)]3+ was instantly generated showing multimodal motion and autonomous return to 1 and 2. In the dissipative process, catenate [Ag(1)]+ ⋅ [Ag3(2)]3+ cleanly transformed into the follow‐up transient device (1) ⋅ [Ag3(2)]3+ exhibiting only sliding motion. Two interference‐free dissipative cycles proved the resilience and robustness of the process. Not one, not two, not three, but four! Filling four receptor sites with Ag+ as chemical fuel is the key to the transient and successive self‐assembly of two multicomponent devices. While the first device displays two nanomechanical movements (shuttling and sliding), the second exhibits a sliding motion at increased speed.