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

doi:10.1021/acs.jpclett.9b02923

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 journal › Article › peer-review

19 Scopus citations

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 language	English (US)
Pages (from-to)	7498-7504
Number of pages	7
Journal	Journal of Physical Chemistry Letters
Volume	10
Issue number	23
DOIs	https://doi.org/10.1021/acs.jpclett.9b02923
State	Published - Dec 5 2019

Funding

We thank Drs. Brian Phelan and Pyosang Kim for useful spectroscopic discussions. This work was supported by the National Science Foundation under grant number DMR-1710104. This material is based upon work supported by the National Science Foundation Graduate Research Fellowship Program under Grant No. DGE-1842165. Any opinions, findings, and conclusions or recommendations expressed in this material are those of the author(s) and do not necessarily reflect the views of the National Science Foundation. We thank Drs. Brian Phelan and Pyosang Kim for useful spectroscopic discussions. This work was supported by the National Science Foundation under grant number DMR-1710104. This material is based upon work supported by the National Science Foundation Graduate Research Fellowship Program under Grant No. DGE-1842165. Any opinions findings, and conclusions or recommendations expressed in this material are those of the author(s) and do not necessarily reflect the views of the National Science Foundation.

ASJC Scopus subject areas

General Materials Science
Physical and Theoretical Chemistry

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title = "Steric Interactions Impact Vibronic and Vibrational Coherences in Perylenediimide Cyclophanes",

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.",

author = "Schultz, {Jonathan D.} and Coleman, {Adam F.} and Aritra Mandal and Shin, {Jae Yoon} and Ratner, {Mark A.} and Young, {Ryan M.} and Wasielewski, {Michael R.}",

note = "Funding Information: We thank Drs. Brian Phelan and Pyosang Kim for useful spectroscopic discussions. This work was supported by the National Science Foundation under grant number DMR-1710104. This material is based upon work supported by the National Science Foundation Graduate Research Fellowship Program under Grant No. DGE-1842165. Any opinions, findings, and conclusions or recommendations expressed in this material are those of the author(s) and do not necessarily reflect the views of the National Science Foundation. Funding Information: We thank Drs. Brian Phelan and Pyosang Kim for useful spectroscopic discussions. This work was supported by the National Science Foundation under grant number DMR-1710104. This material is based upon work supported by the National Science Foundation Graduate Research Fellowship Program under Grant No. DGE-1842165. Any opinions findings, and conclusions or recommendations expressed in this material are those of the author(s) and do not necessarily reflect the views of the National Science Foundation. Publisher Copyright: Copyright {\textcopyright} 2019 American Chemical Society.",

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AU - Ratner, Mark A.

AU - Young, Ryan M.

AU - Wasielewski, Michael R.

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PY - 2019/12/5

Y1 - 2019/12/5

N2 - 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.

AB - 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.

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Steric Interactions Impact Vibronic and Vibrational Coherences in Perylenediimide Cyclophanes

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