Chromophore Dipole Directs Morphology and Photocatalytic Hydrogen Generation

Adam S. Weingarten, Adam J. Dannenhoffer, Roman V. Kazantsev, Hiroaki Sai, Dongxu Huang, Samuel I Stupp

Research output: Contribution to journalArticle

9 Citations (Scopus)


The spontaneous self-assembly of chromophores into light-harvesting antennae provides a potentially low-cost approach to building solar-to-fuel conversion materials. However, designing such supramolecular architectures requires a better understanding of the balance between noncovalent forces among the molecular components. We investigated here the aqueous assembly of perylene monoimide chromophore amphiphiles synthesized with different substituents in the 9-position. The molecular dipole strength decreases as the nature of the substituent is altered from electron donating to electron withdrawing. Compounds with stronger molecular dipoles, in which dipolar interactions stabilize assemblies by 10-15 kJ·mol-1, were found to form crystalline nanoribbons in solution. In contrast, when the molecular dipole moment is small, nanofibers were obtained. Highly blue-shifted absorption maxima were observed in assemblies with large dipoles, indicating strong electronic coupling is present. However, only the moderate dipole compound had the appropriate molecular packing to access charge-transfer excitons leading to enhanced photocatalytic H2 production.

Original languageEnglish
Pages (from-to)4965-4968
Number of pages4
JournalJournal of the American Chemical Society
Issue number15
Publication statusPublished - Apr 18 2018

ASJC Scopus subject areas

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

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