Charge separation mechanisms in ordered films of self-assembled donor-acceptor dyad ribbons

Jenna L. Logsdon, Patrick E. Hartnett, Jordan N. Nelson, Michelle A. Harris, Tobin J. Marks, Michael R. Wasielewski*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

16 Scopus citations


Orthogonal attachment of polar and nonpolar side-chains to a zinc porphyrin-perylenediimide dyad (ZnP-PDI, 1a) is shown to result in self-assembly of ordered supramolecular ribbons in which the ZnP and PDI molecules form segregated π-stacked columns. Following photoexcitation of the ordered ribbons, ZnP+•-PDI-• radical ion pairs form in <200 fs and subsequently produce a 30 ± 3% yield of free charge carriers that live for about 100 μs. Elongating the side chains on ZnP and PDI in 1b enhances the order of the films, but does not result in an increase in free charge carrier yield. In addition, this yield is independent of temperature, free energy of reaction, and the ZnP-PDI distance in the covalent dyad. These results suggest that the free charge carrier yield in this system is not limited by a bound charge transfer (CT) state or promoted by a vibronically hot CT state. Instead, it is likely that π-stacking of the segregated donors and acceptors within the ribbons results in delocalization of the charges following photoexcitation, allowing them to overcome Coulombic attraction and generate free charge carriers.

Original languageEnglish (US)
Pages (from-to)33493-33503
Number of pages11
JournalACS Applied Materials and Interfaces
Issue number39
StatePublished - Oct 4 2017


  • Charge transport
  • Epr
  • Femtosecond transient absorption spectroscopy
  • Giwaxs
  • Organic photovoltaics
  • Self-assembly
  • Thin films

ASJC Scopus subject areas

  • Materials Science(all)


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