Supramolecular polymers in aqueous medium: Rational design based on directional hydrophobic interactions

Alona Ustinov, Haim Weissman, Elijah Shirman, Iddo Pinkas, Xiaobing Zuo, Boris Rybtchinski

Research output: Contribution to journalArticlepeer-review

66 Citations (Scopus)

Abstract

Self-assembly in aqueous medium is of primary importance and widely employs hydrophobic interactions. Yet, unlike directional hydrogen bonds, hydrophobic interactions lack directionality, making difficult rational self-assembly design. Directional hydrophobic motif would significantly enhance rational design in aqueous self-assembly, yet general approaches to such interactions are currently lacking. Here, we show that pairwise directional hydrophobic/π- stacking interactions can be designed using well-defined sterics and supramolecular multivalency. Our system utilizes a hexasubstituted benzene scaffold decorated with 3 (compound 1) or 6 (compound 2) amphiphilc perylene diimides. It imposes a pairwise self-assembly mode, leading to well-defined supramolecular polymers in aqueous medium. the assemblies were characterized using cryogenic electron microscopy, small-angle X-ray scattering, optical spectroscopy, and EPR. Supramolecular polymerization studies in the case of 2 revealed association constants in 10 8 M -1 range, and significant enthalpic contribution to the polymerization free energy. The pairwise PDI motif enables exciton confinement and localized emission in the polymers based on 1 and 2's unique photonic behavior, untypical of the extended π-stacked systems. Directional pairwise hydrophobic interactions introduce a novel strategy for rational design of noncovalent assemblies in aqueous medium, and bring about a unique photofunction.

Original languageEnglish
Pages (from-to)16201-16211
Number of pages11
JournalJournal of the American Chemical Society
Volume133
Issue number40
DOIs
Publication statusPublished - Oct 12 2011

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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