title: Reversible photoswitching of rotaxane character and interplay of thermodynamic stability and kinetic lability in a self-assembling ring-axle molecular system.
abstract: We have designed, synthesized, and investigated a self-assembling system that can be reversibly interconverted between thermodynamically stable (pseudorotaxane) and kinetically inert (rotaxane) forms by light irradiation. The system is composed of a dibenzo[24]crown-8 ring and an axle comprised of a dibenzylammonium recognition site and two azobenzene end groups. The isomeric form of the azobenzene units of the axle has a little influence on the stability constants of the respective pseudorotaxanes but greatly affects the threading-dethreading rate constants. In fact, equilibration of the ring and the axle in its EE isomeric form occurs within seconds in acetonitrile at room temperature, whereas the ZZ axle threads-dethreads the ring at least four orders of magnitude slower. Moreover, we show that a change in the stability of the complex, achieved by deprotonating the dibenzylammonium recognition site on the axle, affects its kinetic behavior. We compare the results of these experiments with those observed upon dethreading the (pseudo)rotaxane by using a competitive guest for the ring, an approach which does not inherently destabilize the ring-axle interaction. This study outlines a general strategy for the reversible photochemical control of motion kinetics in threaded and interlocked compounds and constitutes a starting point for the construction of multicomponent structures that can behave as photochemically driven nanomachines.
authors.affiliation: Dipartimento di Chimica G. Ciamician, Università di Bologna, Via Selmi 2, 40126 Bologna, Italy.
authors.forename: Massimo
authors.initials: M
authors.lastname: Baroncini
authors.forename: Serena
authors.initials: S
authors.lastname: Silvi
authors.forename: Margherita
authors.initials: M
authors.lastname: Venturi
authors.forename: Alberto
authors.initials: A
authors.lastname: Credi