biostudies-literatureDunnebacke TEuropean Research Council10405-10413https://www.ebi.ac.uk/biostudies/studies/S-EPMC8162386biostudies-literatureUnknown11(38)Control over the photochemical outcome of photochromic molecules in solution represents a major challenge, as photoexcitation often leads to multiple competing photochemical and/or supramolecular pathways resulting in complex product mixtures. Herein, we demonstrate precise and efficient control over the photochemical behaviour of cyanostilbenes in solution using a straightforward solvent-controlled approach based on supramolecular polymerization. To this end, we designed a π-extended cyanostilbene bolaamphiphile that exhibits tuneable solvent-dependent photochemical behaviour. Photoirradiation of the system in a monomeric state (in organic solvents) exclusively leads to a highly reversible and efficient E/Z photoisomerization, whereas a nearly quantitative [2 + 2] photocycloChemical scienceSolvent-controlled E/Z isomerization vs. [2 + 2] photocycloaddition mediated by supramolecular polymerization.PMC8162386SUPRACOP-715923715923Kartha KKAlbuquerque RQFernandez GWiest JMDunnebacke TfalseSolvent-controlled E/Z isomerization vs. [2 + 2] photocycloaddition mediated by supramolecular polymerization.Control over the photochemical outcome of photochromic molecules in solution represents a major challenge, as photoexcitation often leads to multiple competing photochemical and/or supramolecular pathways resulting in complex product mixtures. Herein, we demonstrate precise and efficient control over the photochemical behaviour of cyanostilbenes in solution using a straightforward solvent-controlled approach based on supramolecular polymerization. To this end, we designed a π-extended cyanostilbene bolaamphiphile that exhibits tuneable solvent-dependent photochemical behaviour. Photoirradiation of the system in a monomeric state (in organic solvents) exclusively leads to a highly reversible and efficient E/Z photoisomerization, whereas a nearly quantitative [2 + 2] photocyclo2020-01-01T00:00:00Z2020 Sep2025-04-19T15:36:46.793Z2022-02-10T13:49:37.665ZS-EPMC81623863409430110.1039/d0sc03442h