Discordant Supramolecular Fibres Reversibly Depolymerised by Temperature and Light

Marieke Gerth, José Augusto Berrocal, Davide Bochicchio, Giovanni M. Pavan, Ilja K. Voets (Corresponding author)

Research output: Contribution to journalArticleAcademicpeer-review

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.

Original languageEnglish
Number of pages11
JournalChemistry - A European Journal
VolumeXX
Issue numberXX
DOIs
Publication statusAccepted/In press - 11 Nov 2020

Keywords

  • benzene-1,3,5-tricarboxamide
  • photoisomerisation
  • photoswitch
  • responsive
  • supramolecular polymer

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