Steric Interactions Impact Vibronic and Vibrational Coherences in Perylenediimide Cyclophanes

Jonathan D. Schultz, Adam F. Coleman, Aritra Mandal, Jae Yoon Shin, Mark A. Ratner, Ryan M. Young*, Michael R. Wasielewski

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

17 Scopus citations


Designing molecular systems that exploit vibronic coherence to improve light harvesting efficiencies relies on understanding how interchromophoric interactions, such as van der Waals forces and dipolar coupling, influence these coherences in multichromophoric arrays. However, disentangling these interactions requires studies of molecular systems with tunable structural relationships. Here, we use a combination of two-dimensional electronic spectroscopy and femtosecond stimulated Raman spectroscopy to investigate the role of steric hindrance between chromophores in driving changes to vibronic and vibrational coherences in a series of substituted perylenediimide (PDI) cyclophane dimers. We report significant differences in the frequency power spectra from the cyclophane dimers versus the corresponding monomer reference. We attribute these differences to distortion of the PDI cores from steric interactions between the substituents. These results highlight the importance of considering structural changes when rationalizing vibronic coupling in multichromophoric systems.

Original languageEnglish (US)
Pages (from-to)7498-7504
Number of pages7
JournalJournal of Physical Chemistry Letters
Issue number23
StatePublished - Dec 5 2019

ASJC Scopus subject areas

  • General Materials Science
  • Physical and Theoretical Chemistry


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