Excimer Formation and Symmetry-Breaking Charge Transfer in Cofacial Perylene Dimers

Rita E. Cook, Brian T. Phelan, Rebecca J. Kamire, Marek B. Majewski, Ryan M. Young, Michael R Wasielewski

Research output: Contribution to journalArticle

25 Citations (Scopus)

Abstract

The use of multiple chromophores as photosensitizers for catalysts involved in energy-demanding redox reactions is often complicated by electronic interactions between the chromophores. These interchromophore interactions can lead to processes, such as excimer formation and symmetry-breaking charge separation (SB-CS), that compete with efficient electron transfer to or from the catalyst. Here, two dimers of perylene bound either directly or through a xylyl spacer to a xanthene backbone were synthesized to probe the effects of interchromophore electronic coupling on excimer formation and SB-CS using ultrafast transient absorption spectroscopy. Two time constants for excimer formation in the 1-25 ps range were observed in each dimer due to the presence of rotational isomers having different degrees of interchromophore coupling. In highly polar acetonitrile, SB-CS competes with excimer formation in the more weakly coupled isomers followed by charge recombination with τCR = 72-85 ps to yield the excimer. The results of this study of perylene molecular dimers can inform the design of chromophore-catalyst systems for solar fuel production that utilize multiple perylene chromophores. (Figure Presented).

Original languageEnglish
Pages (from-to)1607-1615
Number of pages9
JournalJournal of Physical Chemistry A
Volume121
Issue number8
DOIs
Publication statusPublished - Mar 2 2017

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Perylene
excimers
Chromophores
Dimers
Charge transfer
broken symmetry
dimers
charge transfer
chromophores
polarization (charge separation)
Isomers
Catalysts
Xanthenes
catalysts
isomers
fuel production
Photosensitizing Agents
Redox reactions
Absorption spectroscopy
electronics

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Excimer Formation and Symmetry-Breaking Charge Transfer in Cofacial Perylene Dimers. / Cook, Rita E.; Phelan, Brian T.; Kamire, Rebecca J.; Majewski, Marek B.; Young, Ryan M.; Wasielewski, Michael R.

In: Journal of Physical Chemistry A, Vol. 121, No. 8, 02.03.2017, p. 1607-1615.

Research output: Contribution to journalArticle

Cook, Rita E. ; Phelan, Brian T. ; Kamire, Rebecca J. ; Majewski, Marek B. ; Young, Ryan M. ; Wasielewski, Michael R. / Excimer Formation and Symmetry-Breaking Charge Transfer in Cofacial Perylene Dimers. In: Journal of Physical Chemistry A. 2017 ; Vol. 121, No. 8. pp. 1607-1615.
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