Abstract
Translational movement of the macrocycle in two structurally similar bistable [2]rotaxanes, which is induced by a four‐step electrochemical process in solution, has been investigated by using a methodology developed in the preceding article (Chem. Eur. J. 2008, 14, 1107–1116). Both [2]rotaxanes contain a crown ether that can be accommodated by either of two interconnected viologen recognition sites. These sites are substantially different in terms of their affinity towards the crown ether and they possess considerably different electrochemical reduction potentials. The two [2]rotaxanes differ in the length and the rigidity of a bridge that links these sites. A combination of molecular mechanics modelling and NOE spectroscopy data provides information about the conformations of both [2]rotaxanes in the parent oxidation state when the crown ether exclusively populates the strong recognition site. To determine the population of the recognition sites at subsequent stages of reduction, a paramagnetic NMR technique and cyclic voltammetry were used. The key finding is that the flexibility of the connecting bridge element between the recognition sites interferes with shuttling of the crown ether in [2]rotaxanes. It can be demonstrated that the more flexible trimethylene bridge is folded, thus limiting the propensity of the crown ether to shuttle. Consequently, the crown ether populates the original site even in the second reduced state of the flexible [2]rotaxane. On the contrary, in the [2]rotaxane in which two viologen sites are connected by a larger and more rigid p‐terphenylene bridge, the predominant location of the crown ether at the weak recognition site is achieved after just one single electron reduction.