Crystal-Phase Transitions and Photocatalysis in Supramolecular Scaffolds

Roman V. Kazantsev, Adam J. Dannenhoffer, Adam S. Weingarten, Brian T. Phelan, Boris Harutyunyan, Taner Aytun, Ashwin Narayanan, Daniel J. Fairfield, Job Boekhoven, Hiroaki Sai, Andrew Senesi, Pascual I. O’Dogherty, Liam C. Palmer, Michael J. Bedzyk, Michael R Wasielewski, Samuel I Stupp

Research output: Contribution to journalArticle

18 Citations (Scopus)

Abstract

The energy landscape of a supramolecular material can include different molecular packing configurations that differ in stability and function. We report here on a thermally driven crystalline order transition in the landscape of supramolecular nanostructures formed by charged chromophore amphiphiles in salt-containing aqueous solutions. An irreversible transition was observed from a metastable to a stable crystal phase within the nanostructures. In the stable crystalline phase, the molecules end up organized in a short scroll morphology at high ionic strengths and as long helical ribbons at lower salt content. This is interpreted as the result of the competition between electrostatic repulsive forces and attractive molecular interactions. Only the stable phase forms charge-transfer excitons upon exposure to visible light as indicated by absorbance and fluorescence features, second-order harmonic generation microscopy, and femtosecond transient absorbance spectroscopy. Interestingly, the supramolecular reconfiguration to the stable crystalline phase nanostructures enhances photosensitization of a proton reduction catalyst for hydrogen production.

Original languageEnglish
Pages (from-to)6120-6127
Number of pages8
JournalJournal of the American Chemical Society
Volume139
Issue number17
DOIs
Publication statusPublished - May 3 2017

ASJC Scopus subject areas

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

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    Kazantsev, R. V., Dannenhoffer, A. J., Weingarten, A. S., Phelan, B. T., Harutyunyan, B., Aytun, T., Narayanan, A., Fairfield, D. J., Boekhoven, J., Sai, H., Senesi, A., O’Dogherty, P. I., Palmer, L. C., Bedzyk, M. J., Wasielewski, M. R., & Stupp, S. I. (2017). Crystal-Phase Transitions and Photocatalysis in Supramolecular Scaffolds. Journal of the American Chemical Society, 139(17), 6120-6127. https://doi.org/10.1021/jacs.6b13156