Pure and Applied Chemistry

Abstract: Two classes of rotaxanes are described in which photoinduced processes modulate a large-amplitude motion. In the first type, E–Z-isomerization of a fumaric diamide unit to a maleic diamide leads to a substantial weakening of the hydrogen bonds between the diamide and the macrocyclic ring that surrounds it. As a result, the rate of the pirouetting motion is increased approximately by six orders of magnitude. In the second type, intermolecular photoinduced electron transfer is used to induce a reversible shuttling motion on a time scale of microseconds. Medium effects on the rate of shuttling are presented.