Supramolecular polymer transformation: A kinetic study

Jonathan Baram, Haim Weissman, Boris Rybtchinski

Research output: Contribution to journalArticlepeer-review

29 Citations (Scopus)

Abstract

Investigation of supramolecular kinetics is essential for elucidating self-assembly mechanisms. Recently, we reported on a noncovalent system involving a bolaamphiphilic perylene diimide dimer that is kinetically trapped in water but can rearrange into a different, more ordered assembly in water/THF mixtures (Angew. Chem. Int. Ed. 2014, 53, 4123). Here we present a kinetic mechanistic study of this process by employing UV-vis spectroscopy. The transformation exhibits a rapid decrease in the red-shifted absorption band, which is monitored in order to track the kinetics at different temperatures (15-50 °C) and concentrations. Fitting the data with the 1D KJMA (Kolmogorov-Johnson-Mehl-Avrami) model affords the activation parameters. The latter as well as seeding experiments indicates that the transformation occurs without the detachment of covalent units, and that hydration dynamics plays a significant role in nucleation, with entropic factors being dominant. Switching off the transformation, and the formation of off-pathway intermediates were observed upon heating to temperatures above 55 °C. These insights into kinetically controlled supramolecular polymer transformations provide mechanistic information that is needed for a fundamental understanding of noncovalent processes, and the rational design of noncovalent materials.

Original languageEnglish
Pages (from-to)12068-12073
Number of pages6
JournalJournal of Physical Chemistry B
Volume118
Issue number41
DOIs
Publication statusPublished - Oct 16 2014

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films
  • Materials Chemistry

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