Neira, IagoTaticchi, ChiaraNicoli, FedericoCurcio, MassimilianoGarcía, Marcos D.Peinador, CarlosSilvi, SerenaBaroncini, MassimoCredi, Alberto2026-09-252026-09-252025-04-10Neira, I., Taticchi, C., Nicoli, F., Curcio, M., Garcia, M. D., Peinador, C., Silvi, S., Baroncini, M., & Credi, A. (2025). Light-driven ratcheted formation of diastereomeric host-guest systems. Chem, 11(4), 102375. https://doi.org/10.1016/j.chempr.2024.11.0132451-9294https://hdl.handle.net/2183/49446[Abstract] The ability to exploit an energy source to drive chemical reactions away from thermodynamic equilibrium is anessential feature of life and a grand challenge for the design of fuel-driven dynamic artificial nanosystems. Here,weinvestigatetheeffectoflightirradiationontheformationofsupramolecularcomplexescomposedof azobenzene-type guests and a cyclodextrin (CD) host in water. Whereas previous studies on these complexeshavefocusedonequilibriumproperties,ourworkexploresfar-from-equilibriumdistributionsobtained by light-driven association. We demonstrate that the relative abundance of the two CD orientational diastereomeric complexes can be inverted upon photoirradiation and showcase a ratcheted approach, employing biocompatible macrocycles and harnessing visible light, to the spontaneous formation of high-energy CD complexes with broad applicability in aqueous environments. We foresee opportunities for the development of active materials, the design of artificial metabolic networks, and the engineering of molecular machines operating under physiological conditions.engAttribution-NonCommercial-NoDerivatives 4.0 Internationalhttp://creativecommons.org/licenses/by-nc-nd/4.0/AzobenzeneCyclodextrinCurtin-Hammett principleKinetic asymmetryLight-driven self-assemblyOut of equilibriumRatcheting synthesisRotaxaneSupramolecular complexMolecular machinejournal articleopen access10.1016/j.chempr.2024.11.013