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Depolymerization of supramolecular polymers by a covalent reaction; transforming an intercalator into a sequestrator
Kasper M Vonk1, E W Meijer1, Ghislaine Vantomme1
1Institute for Complex Molecular Systems, Laboratory of Macromolecular and Organic Chemistry, Eindhoven University of Technology P.O. Box 513 5600 MB Eindhoven The Netherlands g.vantomme@tue.nl.
Chemical Science
|November 15, 2021
Summary
A thiol-ene reaction triggers depolymerization of supramolecular polymers. This covalent reaction controls the disassembly of benzene-1,3,5-tricarboxamide (BTA) based assemblies, enabling temporal control over molecular structures.
Area of Science:
- Supramolecular Chemistry
- Polymer Chemistry
- Organic Chemistry
Background:
- Controlling supramolecular assembly and disassembly is key for molecular complexity.
- Covalent reactions can be used to trigger changes in supramolecular structures.
- Benzene-1,3,5-tricarboxamide (BTA) monomers can form self-assembled polymers.
Purpose of the Study:
- To investigate the effect of an in situ thiol-ene reaction on the depolymerization of supramolecular assemblies.
- To explore how covalent reactions influence supramolecular polymerization and disassembly.
- To demonstrate temporal control over depolymerization using reactive monomers.
Main Methods:
- Synthesis of benzene-1,3,5-tricarboxamide (BTA) monomers with cysteine, hexylcysteine, and alkyl side chains (Cys-BTA, HexCys-BTA, a-BTA).
- In situ thiol-ene click chemistry reaction to trigger depolymerization.
- Time-resolved spectroscopy and light scattering for structural analysis and mechanism elucidation.
Main Results:
- Long supramolecular polymers of Cys-BTA were depolymerized into short dimeric aggregates of HexCys-BTA via the in situ thiol-ene reaction.
- The thiol-ene reaction induced depolymerization of an unreactive polymer when Cys-BTA monomers were intercalated.
- Fast dynamics and depolymerization mechanisms were revealed through spectroscopic and scattering analyses.
Conclusions:
- Implementation of reactivity within supramolecular assemblies allows for temporal control of depolymerization.
- The interplay between non-covalent and covalent chemistry is crucial for dynamic molecular systems.
- Thiol-ene reactions serve as effective triggers for controlled supramolecular disassembly.
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