Tunable self-assembly of triazole-linked porphyrin-polymer conjugates

Derrick A Roberts, Timothy W. Schmidt, Maxwell J. Crossley, Sebastien Perrier

Research output: Contribution to journalArticleResearchpeer-review

30 Citations (Scopus)

Abstract

The convergence of supramolecular chemistry and polymer science offers many powerful approaches for building functional nanostructures with well-defined dynamic behaviour. Herein we report the efficient "click" synthesis and self-assembly of AB2- and AB4-type multitopic porphyrin-polymer conjugates (PPCs). PPCs were prepared using the copper(I)-catalysed azide-alkyne cycloaddition (CuAAC) reaction, and consisted of linear polystyrene, poly(butyl acrylate), or poly(tert-butyl acrylate) arms attached to a zinc(II) porphyrin core via triazole linkages. We exploit the presence of the triazole groups obtained from CuAAC coupling to direct the self-assembly of the PPCs into short oligomers (2-6 units in length) via intermolecular porphyrinatozinc-triazole coordination. By altering the length and grafting density of the polymer arms, we demonstrate that the association constant of the porphyrinatozinc-triazole complex can be systematically tuned over two orders of magnitude. Self-assembly of the PPCs also resulted in a 6a K increase in the glass transition temperature of the bulk material compared to a non-assembling PPC. The modular synthesis and tunable self-assembly of the triazole-linked PPCs thus represents a powerful supramolecular platform for building functional nanostructured materials. Tunable building blocks: Triazole-linked porphyrin-polymer conjugates (PPCs) were prepared in high yield using the copper(I)-catalysed azide-alkyne cycloaddition (CuAAC) "click" reaction. The triazole groups were introduced from CuAAC coupling to guide the self-assembly of the PPCs into short oligomers (2-6 units in length) via intermolecular porphyrinatozinc-triazole coordination. Association constants of the PPCs could be tuned by altering the polymer microenvironment around the porphyrin core, thus presenting a modular platform for designing self-assembled porphyrin-polymer materials. 

Original languageEnglish
Pages (from-to)12759-12770
Number of pages12
JournalChemistry - A European Journal
Volume19
Issue number38
DOIs
Publication statusPublished - 16 Sep 2013
Externally publishedYes

Keywords

  • click chemistry
  • cycloaddition
  • polymerization
  • porphyrins
  • supramolecular chemistry

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