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- Title
Discordant Supramolecular Fibres Reversibly Depolymerised by Temperature and Light.
- Authors
Gerth, Marieke; Berrocal, José Augusto; Bochicchio, Davide; Pavan, Giovanni M.; Voets, Ilja K.
- Abstract
Synthetic stimuli responsive supramolecular polymers attract increasing interest for their ability to mimic the unique properties of natural assemblies. Here we focus on the well‐studied benzene‐1,3,5‐tricarboxamide (BTA) motif, and substitute it with two (S)‐3,7‐dimethyloctyl groups and an azobenzene photoswitch. We demonstrate the UV (λ=365 nm) induced depolymerisation of the helical hydrogen‐bonded polymers in methylcyclohexane (MCH) through circular dichroism and UV‐vis spectroscopy in dilute solution (15 μm), and NMR and iPAINT super‐resolution microscopy in concentrated solution (300 μm). The superstructure can be regenerated after thermal depolymerization, whilst repeated depolymerisation can be reversed without degradation by irradiating at λ=455 nm. Molecular dynamics simulations show that the most energetically favourable configuration for these polymers in MCH is a left‐handed helical network of hydrogen‐bonds between the BTA cores surrounded by two right‐handed helices of azobenzenes. The responsiveness to two orthogonal triggers across a broad concentration range holds promise for use in, for example, photo‐responsive gelation.
- Subjects
SUPRAMOLECULAR polymers; MOLECULAR dynamics; SUPRAMOLECULAR chemistry; DEPOLYMERIZATION; CIRCULAR dichroism; GELATION; FIBERS
- Publication
Chemistry - A European Journal, 2021, Vol 27, Issue 5, p1829
- ISSN
0947-6539
- Publication type
Article
- DOI
10.1002/chem.202004115