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

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

J Phys Chem A

Department of Chemistry and Argonne-Northwestern Solar Energy Research (ANSER) Center, Northwestern University, Evanston, Illinois 60208-3113, United States.

Published: March 2017

AI Article Synopsis

Article 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 τ = 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.

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Source
http://dx.doi.org/10.1021/acs.jpca.6b12644DOI Listing

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