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

Research output: Contribution to journalArticle

Abstract

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
Pages (from-to)7498-7504
Number of pages7
JournalJournal of Physical Chemistry Letters
Volume10
Issue number23
DOIs
Publication statusPublished - Dec 5 2019

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Dimers
dimers
Van der Waals forces
interactions
Chromophores
Power spectrum
chromophores
Raman spectroscopy
power spectra
monomers
Monomers
Spectroscopy
electronics
spectroscopy
perylenediimide

ASJC Scopus subject areas

  • Materials Science(all)
  • Physical and Theoretical Chemistry

Cite this

Steric Interactions Impact Vibronic and Vibrational Coherences in Perylenediimide Cyclophanes. / Schultz, Jonathan D.; Coleman, Adam F.; Mandal, Aritra; Shin, Jae Yoon; Ratner, Mark A.; Young, Ryan M.; Wasielewski, Michael R.

In: Journal of Physical Chemistry Letters, Vol. 10, No. 23, 05.12.2019, p. 7498-7504.

Research output: Contribution to journalArticle

Schultz, Jonathan D. ; Coleman, Adam F. ; Mandal, Aritra ; Shin, Jae Yoon ; Ratner, Mark A. ; Young, Ryan M. ; Wasielewski, Michael R. / Steric Interactions Impact Vibronic and Vibrational Coherences in Perylenediimide Cyclophanes. In: Journal of Physical Chemistry Letters. 2019 ; Vol. 10, No. 23. pp. 7498-7504.
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